Catalysts for olefin polymerization

ABSTRACT

This invention relates to the field of olefin polymerization catalyst compositions, and methods for the polymerization and copolymerization of olefins, including polymerization methods using a catalyst composition. One aspect of this invention is the formation and use of a catalyst composition comprising a transition metal compound and an activator for olefin polymerization processes.

TECHNICAL FIELD OF THE INVENTION

This invention relates to the field of olefin polymerization catalystcompositions, methods for the polymerization and copolymerization ofolefins using a catalyst composition, and polyolefins.

BACKGROUND OF THE INVENTION

The chemical industry continually develops new olefin polymerizationcatalysts, catalyst activation processes, and methods of making andusing catalysts that will provide enhanced catalytic activities andproduce polymeric materials tailored to specific end uses.

One type of catalyst system comprises so-called single site organometalcompounds, particularly metallocene compounds and transition metalcompounds. Metallocenes have been well explored, but less is known aboutthe polymerization behavior of transition metal compounds. It isbelieved that transition metal compounds, those compounds that do nothave a cyclopentadienyl, indenyl, fluorenyl, substitutedcyclopentadienyl, substituted indenyl, or substituted fluorenyl groupbound to the metal atom and are thus not metallocenes, may offer thepotential to produce polymers with improved properties, as well as lowercost. Also of interest is the development of transition metalcompound-based catalytic systems that can be activated with a variety ofactivating agents without requiring the use of relatively expensivealuminoxane or borate co-catalysts, yet still provide relatively highpolymerization activities.

Therefore, new catalyst compositions and methods of making the catalystcompositions are needed to afford high polymerization activities, and toallow polymer properties to be designed within the specification rangesfor the desired end-use application.

SUMMARY OF THE INVENTION

This invention comprises catalyst compositions, methods for preparingcatalyst compositions, and methods for polymerizing olefins and usingthe catalyst compositions disclosed herein. The present inventionencompasses new catalyst compositions comprising transition metalcompounds of the following general formula:

wherein:M is titanium, zirconium, or hafnium;R_(n) is an alkyl, aryl, alkaryl or arylaryl group, anyone of which have1-20 carbon atoms;n is 0 or 1;X is independently N, O, P or S;E is a divalent bridging group linking X and Y;Y is independently N, O, P or S;a is 1, 2, 3, or 4;Z is a monovalent anionic group;Z is a monovalent anionic group;b is 0, 1 or 2, and c is 0, 1 or 2;L is a neutral donor ligand; andd is 0, 1 or 2.

In one aspect, the catalyst composition of this invention comprises atransition metal complex and an activator. Several different activatorsmay be used to activate the transition metal compounds of this inventionincluding, but not limited to, an aluminoxane, an organoboron compound,a clay material, an ionizing ionic compound, an ion-exchangeable layeredcompound exchanged with an electron-withdrawing anion, achemically-treated solid oxide compound, a chemically-treated solidoxide compound combined with an organoaluminum compound, or a mixture ofany or all of these activator components.

In another aspect of this invention, the activator comprises achemically-treated solid oxide, which comprises a solid oxide treatedwith an electron-withdrawing anion. In yet another aspect of thisinvention, the activator comprises a chemically-treated solid oxide incombination with an organoaluminum compound.

In still another aspect, the catalyst composition of this inventioncomprises:

a) a transition metal compound;

b) a chemically-treated solid oxide comprising a solid oxide treatedwith an electron-withdrawing anion, wherein

the solid oxide is silica, alumina, silica-alumina, aluminum phosphate,heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide,mixed oxides thereof, or mixtures thereof, and

the electron-withdrawing anion is fluoride, chloride, bromide,phosphate, triflate, bisulfate, sulfate, or combinations thereof; and

c) an organoaluminum compound with the following formula:Al(X⁵)_(n)(X⁶)_(3-n);wherein (X⁵) is a hydrocarbyl having from 1 to about 20 carbon atoms;(X⁶) is an alkoxide or aryloxide, any one of which having from 1 toabout 20 carbon atoms, halide, or hydride; and n is a number from 1 to3, inclusive.

In another aspect of this invention, for example, the transition metalcompound is prepared and is employed along with triisobutylaluminumcocatalyst and a chemically-treated solid oxide comprising fluoridedsilica-alumina, sulfated alumina, or chlorided alumina. Further, thechemically-treated solid oxide optionally contains another metal ormetal ion, including but not limited to, zinc. As used herein thechemically-treated solid oxide is also termed an “activator-support”, ofwhich fluorided silica-alumina, sulfated, and chlorided alumina areexamples. Not wishing to be bound by theory, it is believed that theacidic activator-support is not merely an inert support component of thecatalyst composition, but is involved in effecting the observedcatalytic chemistry.

This invention also encompasses methods of making catalyst compositionsthat comprise contacting at least one transition metal compound and anactivator, including but not limited to, an organoaluminum compoundcombined with a chemically-treated solid oxide. These methods alsocomprise contacting the transition metal compound catalyst, theorganoaluminum cocatalyst, and the chemically-treated solid oxide, andoptionally pretreating some or all of these components with an olefincompound, prior to initiating a polymerization reaction.

The present invention further comprises methods for polymerizing olefinscomprising contacting at least one olefin monomer and a catalystcomposition under polymerization conditions to produce the polymer.

Another aspect of this invention is the polyolefins described herein.

This invention also encompasses an article that comprises the polymerproduced with the catalyst composition of this invention.

These and other features, aspects, embodiments, and advantages of thepresent invention will become apparent after a review of the followingdetailed description of the disclosed features.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides new catalyst compositions, methods forpreparing catalyst compositions, and methods for using the catalystcompositions to polymerize olefins. In accordance with this invention,the catalyst composition comprises at least one transition metalcompound and an activator. The activator of this invention is typicallyan aluminoxane, an organoboron compound, an ionizing ionic compound, aclay material, a chemically-treated solid oxide, a chemically-treatedsolid oxide combined with an organoaluminum compound, or any combinationthereof.

In accordance with this invention, when the activator is a combinationor mixture of a chemically-treated solid oxide and an organoaluminumcompound, the solid oxide has been treated with an electron-withdrawinganion from an ionic or molecular species, or from a source compound ofany type, and optionally treated with another metal in addition to anelectron-withdrawing anion.

Catalyst Composition—The Transition metal Compound

The present invention provides new catalyst compositions comprisingtransition metal compounds, and new methods for polymerizing olefins. Inone aspect, this invention provides catalyst compositions comprising oneor more transition metal compound and an activator component. In oneaspect, the transition metal compound of this invention comprises acompound having the following general formula:

wherein:

M is titanium, zirconium, or hafnium;

the group

is an anionic group selected from cyclodiphosphazanes, bis-phenoxides,N-alkoxy-β-ketoiminates, bis(phenoxy)diamides, diamidoamines,β-Diketonates, cyclodisilazanes, anilidoboranes, diamides, tridentatediamides, pyridine diamides, β-diketiminates, β-ketoiminates,amidinates, salicylaldiminates, substituted cyclodiphosphazanes,substituted bis-phenoxides, substituted N-alkoxy-β-ketoiminates,substituted bis(phenoxy)diamides, substituted diamidoamines, substitutedβ-Diketonates, substituted cyclodisilazanes, substituted anilidoboranes,substituted diamides, substituted tridentate diamides, substitutedpyridine diamides, substituted β-diketiminates, substitutedβ-ketoiminates, substituted amidinates, substituted salicylaldiminates,and mixtures thereof;

a is an integer from 1-4;

(Z) and (Z′) are independently an aliphatic group, an aromatic group, acyclic group, a combination of aliphatic and cyclic groups, an oxygengroup, a sulfur group, a nitrogen group, a phosphorus group, an arsenicgroup, a carbon group, a silicon group, a germanium group, a tin group,a lead group, a boron group, an aluminum group, an inorganic group, anorganometallic group, or a substituted derivative thereof, any one ofwhich having from 1 to about 20 carbon atoms; or a halide;

b is 0, 1 or 2, and c is 0, 1 or 2;

L is a neutral donor ligand; and

d is 0, 1 or 2.

In another aspect of the invention, a transition metal compound offormula

wherein

M is titanium, zirconium, or hafnium;

X is independently nitrogen, oxygen, phosphorus or sulfur;

Y is independently nitrogen, oxygen, phosphorus or sulfur;

each substituent R_(n) on X or Y is independently an aliphatic group, anaromatic group, a cyclic group, a combination of aliphatic and cyclicgroups, or a substituted derivative thereof, any one of which havingfrom 1 to about 20 carbon atoms;

the divalent bridging group, E, a group which connects X and Y, isP(NR)₂P, Ar(R)_(w)CH₂(R)_(w)Ar, Ar(R)_(w)S(R)_(w)Ar, C₂H₄NC(R)CH(R)C,Ar(R)_(w)CH₂N(R)C₂H₄N(R)CH₂Ar(R)_(w), C₂H₄NHC₂H₄, C₂H₄N(R)C₂H₄,Si(R)(NR)₂(R)Si, C(R¹)C(R²)C(R¹), B(NR₂)(NR₂)B, C₃H₆, C₂H₄OC₂H₄,CH₂(C₅H₃N)CH₂, C(R²)C(R³)C(R²), C(R′), or CHAr(R)_(w),

wherein R, R¹, R², R³, or R′, is independently an alkyl, cycloalkyl,aryl, aralkyl, substituted alkyl, substituted aryl, or substitutedaralkyl, any one of which having from 1 to about 20 carbon atoms,wherein Ar is an aromatic group and (R)_(w) is independently analiphatic group, an aromatic group, a cyclic group, a combination ofaliphatic and cyclic groups, or a substituted derivative thereof, anyone of which having from 1 to about 20 carbon atoms, and where w is from0-5;

(Z) and (Z′) are independently an aliphatic group, an aromatic group, acyclic group, a combination of aliphatic and cyclic groups, an oxygengroup, a sulfur group, a nitrogen group, a phosphorus group, an arsenicgroup, a carbon group, a silicon group, a germanium group, a tin group,a lead group, a boron group, an aluminum group, an inorganic group, anorganometallic group, or a substituted derivative thereof, any one ofwhich having from 1 to about 20 carbon atoms; or a halide.

Examples of aliphatic groups, in each instance, include, but are notlimited to, an alkyl group, a cycloalkyl group, an alkenyl group, acycloalkenyl group, an alkynyl group, an alkadienyl group, a cyclicgroup, and the like, and includes all substituted, unsubstituted,branched, and linear analogs or derivatives thereof, in each instancehaving from one to about 20 carbon atoms. Thus, aliphatic groupsinclude, but are not limited to, hydrocarbyls such as paraffins andalkenyls. For example, aliphatic groups as used herein include methyl,ethyl, propyl, n-butyl, tert-butyl, sec-butyl, isobutyl, amyl, isoamyl,hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, dodecyl, 2-ethylhexyl,pentenyl, butenyl, and the like.

Examples of aromatic groups, in each instance, include, but are notlimited to, phenyl, naphthyl, anthracenyl, and the like, includingsubstituted derivatives thereof, in each instance having from 6 to about25 carbons. Substituted derivatives of aromatic compounds include, butare not limited to, tolyl, xylyl, mesityl, and the like, including anyheteroatom substituted derivative thereof.

Examples of cyclic groups, in each instance, include, but are notlimited to, cycloparaffins, cycloolefins, cycloacetylenes, arenes suchas phenyl, bicyclic groups and the like, including substitutedderivatives thereof, in each instance having from about 3 to about 20carbon atoms.

Examples of halides, in each instance, include fluoride, chloride,bromide, and iodide.

In each instance, oxygen groups are oxygen-containing groups, examplesof which include, but are not limited to, alkoxy or aryloxy groups(—OR), —OC(O)R, —OC(O)H, —OSiR₃, —OPR₂, —OAlR₂, and the like, includingsubstituted derivatives thereof, wherein R in each instance is an alkyl,cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, orsubstituted aralkyl having from 1 to about 20 carbon atoms. Examples ofalkoxy or aryloxy groups (—OR) groups include, but are not limited to,methoxy, ethoxy, propoxy, butoxy, phenoxy, substituted phenoxy, and thelike.

In each instance, sulfur groups are sulfur-containing groups, examplesof which include, but are not limited to, —SR, —OSO₂R, —OSO₂OR, —SCN,—SO₂R, and the like, including substituted derivatives thereof, whereinR in each instance is an alkyl, cycloalkyl, aryl, aralkyl, substitutedalkyl, substituted aryl, or substituted aralkyl having from 1 to about20 carbon atoms.

In each instance, nitrogen groups are nitrogen-containing groups, whichinclude, but are not limited to, —NH₂, —NHR, —NR₂, —NO₂, —N₃, and thelike, including substituted derivatives thereof, wherein R in eachinstance is an alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl,substituted aryl, or substituted aralkyl having from 1 to about 20carbon atoms.

In each instance, phosphorus groups are phosphorus-containing groups,which include, but are not limited to, —PH₂, —PHR, —PR₂, —P(O)R₂,—P(OR)₂, —P(O)(OR)₂, and the like, including substituted derivativesthereof, wherein R in each instance is an alkyl, cycloalkyl, aryl,aralkyl, substituted alkyl, substituted aryl, or substituted aralkylhaving from 1 to about 20 carbon atoms.

In each instance, arsenic groups are arsenic-containing groups, whichinclude, but are not limited to, —AsHR, —AsR₂, —As(O)R₂, —As(OR)₂,—As(O)(OR)₂, and the like, including substituted derivatives thereof,wherein R in each instance is selected from alkyl, cycloalkyl, aryl,aralkyl, substituted alkyl, substituted aryl, or substituted aralkylhaving from 1 to about 20 carbon atoms.

In each instance, carbon groups are carbon-containing groups, whichinclude, but are not limited to, alkyl halide groups that comprisehalide-substituted alkyl groups with 1 to about 20 carbon atoms, aralkylgroups with 1 to about 20 carbon atoms, —C(O)H, —C(O)R, —C(O)OR, cyano,—C(NR)H, —C(NR)R, —C(NR)OR, and the like, including substitutedderivatives thereof, wherein R in each instance is an alkyl, cycloalkyl,aryl, aralkyl, substituted alkyl, substituted aryl, or substitutedaralkyl having from 1 to about 20 carbon atoms.

In each instance, silicon groups are silicon-containing groups, whichinclude, but are not limited to, silyl groups such alkylsilyl groups,arylsilyl groups, arylalkylsilyl groups, siloxy groups, and the like,which in each instance have from 1 to about 20 carbon atoms. Forexample, silicon groups include trimethylsilyl and phenyloctylsilylgroups.

In each instance, germanium groups are germanium-containing groups,which include, but are not limited to, germyl groups such alkylgermylgroups, arylgermyl groups, arylalkylgermyl groups, germyloxy groups, andthe like, which in each instance have from 1 to about 20 carbon atoms.

In each instance, tin groups are tin-containing groups, which include,but are not limited to, stannyl groups such alkylstannyl groups,arylstannyl groups, arylalkylstannyl groups, stannoxy (or “stannyloxy”)groups, and the like, which in each instance have from 1 to about 20carbon atoms.

In each instance, lead groups are lead-containing groups, which include,but are not limited to, alkyllead groups, aryllead groups, arylalkylleadgroups, and the like, which in each instance, have from 1 to about 20carbon atoms.

In each instance, boron groups are boron-containing groups, whichinclude, but are not limited to, —BR₂, —BX₂, —BRX, wherein X is amonoanionic group such as halide, hydride, alkoxide, alkyl thiolate, andthe like, and wherein R in each instance is an alkyl, cycloalkyl, aryl,aralkyl, substituted alkyl, substituted aryl, or substituted aralkylhaving from 1 to about 20 carbon atoms.

In each instance, aluminum groups are aluminum-containing groups, whichinclude, but are not limited to, —AlR₂, —AlX₂, —AlRX, wherein X is amonoanionic group such as halide, hydride, alkoxide, alkyl thiolate, andthe like, and wherein R in each instance is an alkyl, cycloalkyl, aryl,aralkyl, substituted alkyl, substituted aryl, or substituted aralkylhaving from 1 to about 20 carbon atoms.

Examples of inorganic groups that may be used as substituents, in eachinstance, include, but are not limited to, —SO₂X, —OAlX₂, —OSiX₃, —OPX₂,—SX, —OSO₂X, —AsX₂, —As(O)X₂, —PX₂, and the like, wherein X is amonoanionic group such as halide, hydride, amide, alkoxide, alkylthiolate, and the like, and wherein any alkyl, cycloalkyl, aryl,aralkyl, substituted alkyl, substituted aryl, or substituted aralkylgroup or substituent on these ligands has from 1 to about 20 carbonatoms.

Examples of organometallic groups that may be used as substituents, ineach instance, include, but are not limited to, organoboron groups,organoaluminum groups, organogallium groups, organosilicon groups,organogermanium groups, organotin groups, organolead groups,organo-transition metal groups, and the like, having from 1 to about 20carbon atoms.

In one aspect of this invention, (Z) and (Z′) are independentlyselected, and include, but are not limited to, the following groups andtheir substituted derivatives: halides, alkoxides having from 1 to about10 carbon atoms, or hydrocarbyls having from 1 to about 10 carbon atoms.In another aspect of this invention, (Z) and (Z′) are chloro, bromo,methyl, benzyl, or trifluoromethyl sulfonyl. In yet another aspect, (Z)and (Z′) are chloro.

In one aspect, a is 0, 1, 2, 3, or 4; b is 0, 1 or 2, and c is 0, 1 or2, such that the valence of a+b+c equals the valence of M;

L can be any neutral donor ligand that does not materially interferewith the activation and polymerization activity of the catalystcompositions of this invention. Typically, the donor ligand L is anether, furan or nitrile. The neutral donor ligand L can be diethylether,tetrahydrofuran or acetonitrile, most preferably diethylether,tetrahydrofuran, and d can be 0, 1, or 2.

Numerous processes to prepare transition metal compounds that can beemployed in this invention have been reported. For example, thesynthesis of exemplary transition metal compounds can be found in:Grochall, L., Stahl, L., Staples, R. J., J. Chem. Soc., Chem. Commun.1997, 1465; Okuda, J., Fokken, S., Kang, H., Massa, W., Chem. Ber. 1995,128, 221; van der Linden, A., Schaverien, C. J., Meijboom, N., Ganter,C., Orpen, A. G., J. Am. Chem. Soc. 1995, 117(11), 3008; Doherty, S.,Errington, R. J., Houssley, N., Ridland, J., Clegg, W., Elsegood, M. R.J., Organometallics, 1999, 18(6), 1018; Tshuva, E. Y., Goldberg, I.,Kol, M., J. Am. Chem. Soc. 2000, 122(43), 10706; Schrock, R. R., Casado,A. L., Goodman, J. T., Liang, L., Bonitatebus Jr, P. J., Davis, W. M.,Organometallics, 2000, 19, 5325; Jensen, M. J., Farmer, K. R., U.S. Pat.No. 6,380,329; and Gibson, V. C., Spitzmesser, S. K., Chem. Rev. 2003,103, 283-315, and references therein; the disclosures of which areincorporated herein by reference in their entirety.

Examples of such transition metal compounds that are useful in thepresent invention include, but are not limited to, the followingcompounds:

and the like.Catalyst Composition—The Activator

In addition to the transition metal compounds disclosed herein, thecatalyst composition of this invention further comprises an activator.In one aspect of this invention, the activator is an aluminoxane, anorganoboron compound, an ionizing ionic compound, a clay material, achemically-treated solid oxide, a chemically-treated solid oxidecombined with an organoaluminum compound, or any combination thereof. Inanother aspect of the invention, the clay material is selected fromclays and other natural and synthetic layered oxides, an exfoliatedclay, an exfoliated clay gelled into another oxide matrix, a layeredsilicate mineral, a non-layered silicate mineral, a layeredaluminosilicate mineral, a non-layered aluminosilicate mineral, cogelledclay matrices containing silica or other oxides, pillared clays,zeolites, clay minerals, other layered minerals, or combinationsthereof, including, but not limited to, ion-exchangeable layeredminerals (natural or synthetic) or composites made from such compounds,regardless of whether the layered structure remains intact or not. Theactivator may further comprise a combination or mixture of any of theseactivators.

The Chemically-Treated Solid Oxide

In one aspect, the present invention encompasses catalyst compositionscomprising a chemically-treated solid oxide which serves as an acidicactivator-support, and which is typically used in combination with anorganoaluminum compound. In one aspect, the chemically treated solidoxide comprises a solid oxide treated with an electron-withdrawinganion; wherein the solid oxide is silica, alumina, silica-alumina,aluminum phosphate, heteropolytungstates, titania, zirconia, magnesia,boria, zinc oxide, mixed oxides thereof, or mixtures thereof; andwherein the electron-withdrawing anion is fluoride, chloride, bromide,phosphate, triflate, bisulfate, sulfate, or any combination thereof.

The chemically-treated solid oxide includes the contact product of atleast one solid oxide compound and at least one electron-withdrawinganion source. In one aspect, the solid oxide compound comprises aninorganic oxide. It is not required that the solid oxide compound becalcined prior to contacting the electron-withdrawing anion source. Thecontact product may be calcined either during or after the solid oxidecompound is contacted with the electron-withdrawing anion source. Inthis aspect, the solid oxide compound may be calcined or uncalcined. Inanother aspect, the chemically-treated solid oxide may comprise thecontact product of at least one calcined solid oxide compound and atleast one electron-withdrawing anion source.

The chemically-treated solid oxide exhibits enhanced acidity as comparedto the corresponding untreated solid oxide compound. Thechemically-treated solid oxide also functions as a catalyst activator ascompared to the corresponding untreated solid oxide. While not intendingto be bound by theory, it is believed that the chemically-treated solidoxide may function as an ionizing solid oxide compound by completely orpartially extracting an anionic ligand from the transition metalcompound. However, the chemically-treated solid oxide is an activatorregardless of whether it is ionizes the transition metal compound,abstracts an anionic ligand to form an ion pair, weakens themetal-ligand bond in the transition metal compound, simply coordinatesto an anionic ligand when it contacts the chemically-treated solidoxide, or any other mechanisms by which activation may occur. While thechemically-treated solid oxide activates the transition metal compoundin the absence of cocatalysts, it is not necessary to eliminatecocatalysts from the catalyst composition. The activation function ofthe chemically-treated solid oxide is evident in the enhanced activityof catalyst composition as a whole, as compared to a catalystcomposition containing the corresponding untreated solid oxide. However,it is believed that the chemically-treated solid oxide functions as anactivator, even in the absence of organoaluminum compound, aluminoxanes,organoboron compounds, or ionizing ionic compounds.

In one aspect, the chemically treated solid oxide of this inventioncomprises a solid inorganic oxide material, a mixed oxide material, or acombination of inorganic oxide materials, that is chemically-treatedwith an electron-withdrawing component, and optionally treated with ametal. Thus, the solid oxide of this invention encompasses oxidematerials such as alumina, “mixed oxide” compounds thereof such assilica-alumina, and combinations and mixtures thereof. The mixed oxidecompounds such as silica-alumina are single chemical phases with morethan one metal combined with oxygen to form a solid oxide compound, andare encompassed by this invention.

In one aspect of this invention, the chemically-treated solid oxidefurther comprises a metal or metal ion selected from zinc, nickel,vanadium, silver, copper, gallium, tin, tungsten, molybdenum, or anycombination thereof. Examples of chemically-treated solid oxides thatfurther comprise a metal or metal ion include, but are not limited to,zinc-impregnated chlorided alumina, zinc-impregnated fluorided alumina,zinc-impregnated chlorided silica-alumina, zinc-impregnated fluoridedsilica-alumina, zinc-impregnated sulfated alumina, or any combinationthereof.

In another aspect, the chemically-treated solid oxide of this inventioncomprises a solid oxide of relatively high porosity, which exhibitsLewis acidic or Brønsted acidic behavior. The solid oxide ischemically-treated with an electron-withdrawing component, typically anelectron-withdrawing anion, to form a chemically-treated solid oxide.While not intending to be bound by the following statement, it isbelieved that treatment of the inorganic oxide with anelectron-withdrawing component augments or enhances the acidity of theoxide. Thus, the chemically treated solid oxide exhibits Lewis orBrønsted acidity which is typically greater than the Lewis or Brønstedacidity of the untreated solid oxide. One method to quantify the acidityof the chemically-treated and untreated solid oxide materials is bycomparing the polymerization activities of the treated and untreatedoxides under acid catalyzed reactions.

In one aspect, the chemically-treated solid oxide comprises a solidinorganic oxide comprising oxygen and at least one element selected fromGroup 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 of the periodictable, or comprising oxygen and at least one element selected from thelanthanide or actinide elements. (See: Hawley's Condensed ChemicalDictionary, 11^(th) Ed., John Wiley & Sons; 1995; Cotton, F. A.;Wilkinson, G.; Murillo; C. A.; and Bochmann; M. Advanced InorganicChemistry, 6^(th) Ed., Wiley-Interscience, 1999.) Usually, the inorganicoxide comprises oxygen and at least one element selected from Al, B, Be,Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V,W, P, Y, Zn or Zr.

Suitable examples of solid oxide materials or compounds that can be usedin the chemically-treated solid oxide of the present invention include,but are not limited to, Al₂O₃, B₂O₃, BeO, Bi₂O₃, CdO, Co₃O₄, Cr₂O₃, CuO,Fe₂O₃, Ga₂O₃, La₂O₃, Mn₂O₃, MoO₃, NiO, P₂O₅, Sb₂O₅, SiO₂, SnO₂, SrO,ThO₂, TiO₂, V₂O₅, WO₃, Y₂O₃, ZnO, ZrO₂, and the like, including mixedoxides thereof, and combinations thereof. Examples of mixed oxides thatcan be used in the chemically-treated solid oxide of the presentinvention include, but are not limited to, silica-alumina,silica-titania, silica-zirconia, zeolites, clays, alumina-titania,alumina-zirconia, aluminum phosphate, heteropolytungstates, and thelike.

In one aspect of this invention, the solid oxide material ischemically-treated by contacting it with at least oneelectron-withdrawing component, typically an electron-withdrawing anionsource. Further, the solid oxide material is optionally chemicallytreated with a metal ion, then calcined to form a metal-containing ormetal-impregnated chemically treated solid oxide. Alternatively, a solidoxide material and an electron-withdrawing anion source are contactedand calcined simultaneously. The method by which the oxide is contactedwith an electron-withdrawing component, typically a salt or an acid ofan electron-withdrawing anion, includes, but is not limited to, gelling,co-gelling, impregnation of one compound onto another, and the like.Typically, following any contacting method, the contacted mixture ofoxide compound, electron-withdrawing anion, and optionally the metal ionis calcined.

The electron-withdrawing component used to treat the oxide is anycomponent that increases the Lewis or Brønsted acidity of the solidoxide upon treatment. In one aspect, the electron-withdrawing componentis an electron-withdrawing anion derived from a salt, an acid, or othercompound such as a volatile organic compound that may serve as a sourceor precursor for that anion. Examples of electron-withdrawing anionsinclude, but are not limited to, sulfate, bisulfate, fluoride, chloride,bromide, iodide, fluorosulfate, fluoroborate, phosphate,fluorophosphate, trifluoroacetate, triflate, fluorozirconate,fluorotitanate, trifluoroacetate, triflate, and the like, includingmixtures and combinations thereof. In addition, other ionic or non-ioniccompounds that serve as sources for these electron-withdrawing anionsmay also be employed in the present invention.

When the electron-withdrawing component comprises a salt of anelectron-withdrawing anion, the counterion or cation of that salt may beany cation that allows the salt to revert or decompose back to the acidduring calcining. Factors that dictate the suitability of the particularsalt to serve as a source for the electron-withdrawing anion include,but are not limited to, the solubility of the salt in the desiredsolvent, the lack of adverse reactivity of the cation, ion-pairingeffects between the cation and anion, hygroscopic properties imparted tothe salt by the cation, and the like, and thermal stability of theanion. Examples of suitable cations in the salt of theelectron-withdrawing anion include, but are not limited to, ammonium,trialkyl ammonium, tetraalkyl ammonium, tetraalkyl phosphonium, H⁺,[H(OEt₂)₂]⁺, and the like.

Further, combinations of one or more different electron-withdrawinganions, in varying proportions, can be used to tailor the specificacidity of the activator-support to the desired level. Combinations ofelectron-withdrawing components may be contacted with the oxide materialsimultaneously or individually, and any order that affords the desiredactivator-support acidity.

Once the solid oxide has been treated and dried, it is subsequentlycalcined. Calcining of the treated solid oxide is generally conducted inan ambient atmosphere, typically in a dry ambient atmosphere, at atemperature from about 200° C. to about 900° C., and for a time of about1 minute to about 100 hours. In another aspect, calcining is conductedat a temperature from about 300° C. to about 800° C. and in anotheraspect, calcining is conducted at a temperature from about 400° C. toabout 700° C. In yet another aspect, calcining is conducted from about 1hour to about 50 hours, and in another aspect calcining is conducted,from about 3 hours to about 20 hours. In still another aspect, when thetreated solid oxide is fluorided silica-alumina, calcining may becarried out from about 1 to about 10 hours at a temperature from about350° C. to about 550° C.

Further, any type of suitable ambient atmosphere can be used duringcalcining. Generally, calcining is conducted in an oxidizing atmosphere,such as air. Alternatively, an inert atmosphere, such as nitrogen orargon, or a reducing atmosphere such as hydrogen or carbon monoxide maybe used.

In another aspect of the invention, the solid oxide component used toprepare the chemically-treated solid oxide has a pore volume greaterthan about 0.1 cc/g. In another aspect, the solid oxide component has apore volume greater than about 0.5 cc/g, and in yet another aspect,greater than about 1.0 cc/g. In still another aspect, the solid oxidecomponent has a surface area from about 100 to about 1000 m²/g. Inanother aspect, solid oxide component has a surface area from about 200to about 800 m^(2x/g, and in still another aspect, from about) 250 toabout 600 m²/g.

The solid oxide material may be treated with a source of halide ion orsulfate ion, or a combination of anions, and optionally treated with ametal ion, then calcined to provide the activator-support in the form ofa particulate solid. Thus, the treated solid oxide component isgenerally a halided or sulfated solid oxide component, a halided or asulfated metal-containing solid oxide component, or a combinationthereof. In one aspect of this invention, the treated solid oxideactivator-support is a treated alumina, treated silica-alumina, ormixtures thereof. In another aspect, the treated alumina is chloridedalumina, bromided alumina, sulfated alumina, fluorided silica-alumina,chlorided alumina or silica-alumina or silica-zirconia, bromidedsilica-alumina, or mixtures thereof, each optionally having been treatedwith a metal ion. In yet another aspect, the treated metal oxide ischlorided alumina, sulfated alumina, fluorided silica-alumina, ormixtures thereof, each optionally having been treated with a metal ion.

In one aspect of this invention, the treated oxide activator-supportcomprises a fluorided solid oxide in the form of a particulate solid,thus a source of fluoride ion is added to the oxide by treatment with afluoriding agent. In still another aspect, fluoride ion may be added tothe oxide by forming a slurry of the oxide in a suitable solvent such asalcohol or water, including, but not limited to, the one to three carbonalcohols because of their volatility and low surface tension. Examplesof fluoriding agents that can be used in this invention include, but arenot limited to, hydrofluoric acid (HF), ammonium fluoride (NH₄F),ammonium bifluoride (NH₄HF₂), ammonium tetrafluoroborate (NH₄BF₄),ammonium silicofluoride (hexafluorosilicate) ((NH₄)₂SiF₆), ammoniumhexafluorophosphate (NH₄ PF₆), analogs thereof, and combinationsthereof. For example, ammonium bifluoride NH₄HF₂ may be used as thefluoriding agent, due to its ease of use and ready availability.

In another aspect of the present invention, the solid oxide can betreated with a fluoriding agent during the calcining step. Anyfluoriding agent capable of thoroughly contacting the solid oxide duringthe calcining step can be used. For example, in addition to thosefluoriding agents described previously, volatile organic fluoridingagents may be used. Examples of volatile organic fluoriding agentsuseful in this aspect of the invention include, but are not limited to,freons, perfluorohexane, perfluorobenzene, fluoromethane,trifluoroethanol, and combinations thereof. Gaseous hydrogen fluoride orfluorine itself can also be used with the solid oxide is fluoridedduring calcining. One convenient method of contacting the solid oxidewith the fluoriding agent is to vaporize a fluoriding agent into a gasstream used to fluidize the solid oxide during calcination.

Similarly, in another aspect of this invention, the chemically treatedsolid oxide comprises a chlorided solid oxide in the form of aparticulate solid, thus a source of chloride ion is added to the oxideby treatment with a chloriding agent. The chloride ion may be added tothe oxide by forming a slurry of the oxide in a suitable solvent. Inanother aspect of the present invention, the solid oxide can be treatedwith a chloriding agent during the calcining step. Any chloriding agentcapable of serving as a source of chloride and thoroughly contacting theoxide during the calcining step can be used. For example, volatileorganic chloriding agents may be used. Examples of volatile organicchloriding agents useful in this aspect of the invention include, butare not limited to, certain freons, perchlorobenzene, chloromethane,dichloromethane, chloroform, carbon tetrachloride, and combinationsthereof. Gaseous hydrogen chloride or chlorine itself can also be usedwith the solid oxide during calcining. One convenient method ofcontacting the oxide with the chloriding agent is to vaporize achloriding agent into a gas stream used to fluidize the solid oxideduring calcination.

In one aspect, the amount of fluoride or chloride ion present beforecalcining the solid oxide is generally from about 2 to about 50% byweight, where the weight percents are based on the weight of the solidoxide, for example silica-alumina, before calcining. In another aspect,the amount of fluoride or chloride ion present before calcining thesolid oxide is from about 3 to about 25% by weight, and in anotheraspect, from about 4 to about 20% by weight. If the fluoride or chlorideion are added during calcining, such as when calcined in the presence ofCCl₄, there is typically no fluoride or chloride ion in the solid oxidebefore calcining. Once impregnated with halide, the halided oxide may bedried by any method known in the art including, but not limited to,suction filtration followed by evaporation, drying under vacuum, spraydrying, and the like, although it is also possible to initiate thecalcining step immediately without drying the impregnated solid oxide.

The silica-alumina used to prepare the treated silica-alumina can have apore volume greater than about 0.5 cc/g. In one aspect, the pore volumemay be greater than about 0.8 cc/g, and in another aspect, the porevolume may be greater than about 1.0 cc/g. Further, the silica-aluminamay have a surface area greater than about 100 m²/g. In one aspect, thesurface area is greater than about 250 m²/g, and in another aspect, thesurface area may be greater than about 350 m²/g. Generally, thesilica-alumina of this invention has an alumina content from about 5 toabout 95%. In one aspect, the alumina content may be from about 5 toabout 50%, and in another aspect, the alumina content may be from about8% to about 30% alumina by weight.

The sulfated solid oxide comprises sulfate and a solid oxide componentsuch as alumina or silica-alumina, in the form of a particulate solid.Optionally, the sulfated oxide is further treated with a metal ion suchthat the calcined sulfated oxide comprises a metal. In one aspect, thesulfated solid oxide comprises sulfate and alumina. In one aspect ofthis invention, the sulfated alumina is formed by a process wherein thealumina is treated with a sulfate source, for example, but not limitedto, sulfuric acid or ammonium sulfate.

In addition to being treated with an electron-withdrawing component suchas halide or sulfate ion, the solid inorganic oxide of this inventionmay optionally be treated with a metal source, including metal salts ormetal-containing compounds. In one aspect of the invention, thesecompounds may be added to or impregnated onto the solid oxide insolution form, and subsequently converted into the supported metal uponcalcining. Accordingly, the solid inorganic oxide can further comprise ametal selected from zinc, nickel, vanadium, silver, copper, gallium,tin, tungsten, molybdenum, or a combination thereof. For example, zincmay be used to impregnate the solid oxide because it provides goodcatalyst activity and low cost. The solid oxide may be treated withmetal salts or metal-containing compounds before, after, or at the sametime that the solid oxide is treated with the electron-withdrawinganion.

Further, any method of impregnating the solid oxide material with ametal may be used. The method by which the oxide is contacted with ametal source, typically a salt or metal-containing compound, includes,but is not limited to, gelling, co-gelling, impregnation of one compoundonto another, and the like. Following any contacting method, thecontacted mixture of oxide compound, electron-withdrawing anion, and themetal ion is typically calcined. Alternatively, a solid oxide material,an electron-withdrawing anion source, and the metal salt ormetal-containing compound are contacted and calcined simultaneously.

One aspect of this invention encompasses a process to produce a catalystcomposition comprises contacting a transition metal dialkyl complex anda sulfated alumina to produce the first catalyst composition.

Another aspect of this invention encompasses a process to produce acatalyst composition comprises contacting transition metal complex, achlorided alumina, or a fluorided silica-alumina, and an organoaluminumcompound selected from triisobutyl aluminum or triethylaluminum toproduce the first catalyst composition.

The preparation of the treated solid oxide activators is described inU.S. Pat. Nos. 6,107,230; 6,165,929; 6,300,271; 6,316,553; 6,355,594;6,376,415; 6,391,816; and 6,395,666; 6,524,987; 6,531,550; 6,548,441;6,548,442; 6,576,583; 6,667,274; 6,750,302 and 6,833,338; each of whichis incorporated herein by reference, in its entirety.

The Organoaluminum Compound

In one aspect, when the activator of the present invention comprises atreated inorganic oxide it may be used in combination with anorganoaluminum compound. Thus, the present invention comprises a methodto prepare a catalyst comprising contacting the transition metalcompound and a treated inorganic oxide with at least one organoaluminumcompound. One aspect of this invention involves the use of someorganoaluminum compound to precontact the other catalyst componentsprior to introducing the catalyst into the polymerization reactor, andthe balance of the organoaluminum compound to be introduced directlyinto the polymerization reactor. It is not required that theorganoaluminum compound used in the optional precontact step with theother catalyst components be the same as the organoaluminum compoundintroduced directly into the polymerization reactor.

Organoaluminum compounds that can be used along with the treated solidoxide to form the activator for a transition metal compound include, butare not limited to compounds having the following general formula:Al(X⁵)_(n)(X⁶)_(3-n);wherein (X⁵) is a hydrocarbyl having from 1 to about 20 carbon atoms;(X⁶) is an alkoxide or aryloxide, any one of which having from 1 toabout 20 carbon atoms, halide, or hydride; and n is a number from 1 to3, inclusive.

In one aspect of this invention, (X⁵) is an alkyl having from 2 to about10 carbon atoms. In another aspect, (X⁵) is ethyl, propyl, n-butyl,sec-butyl, isobutyl, hexyl, and the like.

In another aspect, (X⁶) is an alkoxide or aryloxide, any one of whichhaving from 1 to about 10 carbon atoms, halide, or hydride. In yetanother aspect, (X⁶) is independently fluoro or chloro.

In the formula Al(X⁵)_(n)(X⁶)_(3-n), is a number from 1 to 3 inclusive.In one aspect of this invention, n is 3. The value of n is notrestricted to be an integer, therefore this formula includessesquihalide compounds.

Generally, examples of organoaluminum compounds that can be used in thisinvention include, but are not limited to, trialkylaluminum compounds,dialkylaluminium halide compounds, alkylaluminum dihalide compounds,alkylaluminum sesquihalide compounds, and combinations thereof. Specificexamples of organoaluminum compounds that can be used in this inventionin the precontacted mixture with the organometal compound and an olefinor acetylene monomer include, but are not limited to, trimethylaluminum(TMA); triethylaluminum (TEA); tripropylaluminum; diethylaluminumethoxide; tributylaluminum; diisobutylaluminum hydride;triisobutylaluminum (TIBAL); and diethylaluminum chloride.

One aspect of this invention involves the optional use of some or all ofthe organoaluminum compound to precontact the other catalyst componentsprior to introducing the catalyst into the polymerization reactor. Thebalance of the organoaluminum compound may be introduced directly intothe polymerization reactor. The amounts of organoaluminum compounddisclosed herein include the total amount of organoaluminum compoundused in an optional precontact step, and any additional organoaluminumcompound added in a different step. In one aspect, triethylaluminum(TEA) and triisobutylaluminum (TIBAL) may be used in this aspect of thisinvention.

The Aluminoxane Activator

The present invention provides catalyst compositions comprising one ormore transition metal compounds, and an activator component. In oneaspect, the activator of this invention comprises at least onealuminoxane activator. Aluminoxanes are also referred to aspoly(hydrocarbyl aluminum oxides). In this aspect, the transition metalcompound may be contacted with the aluminoxane in a saturatedhydrocarbon compound solvent, though any solvent which is substantiallyinert to the reactants, intermediates, and products of the activationstep can be used. Thus, in one aspect, the catalyst compositions of thepresent invention comprise the composition that results from reaction ofat least one aluminoxane cocatalyst with at least one transition metalcompound. The catalyst composition formed in this manner may becollected by methods known to those of skill in the art, including butnot limited to filtration, or the catalyst composition may be introducedinto the polymerization reactor without being isolated.

The aluminoxane compound of this invention may be an oligomeric aluminumcompound, wherein the aluminoxane compound can comprise linearstructures, cyclic, or cage structures, or any mixture thereof. Cyclicaluminoxane compounds having the formula:

R is a linear or branched alkyl having from 1 to 10 carbon atoms, and nis an integer from 3 to about 10 are encompassed by this invention. The(AlRO)_(n) moiety shown here also constitutes the repeating unit in alinear aluminoxane. Thus, linear aluminoxanes having the formula:

R is a linear or branched alkyl having from 1 to 10 carbon atoms, and nis an integer from 1 to about 50, are also encompassed by thisinvention.

Further, aluminoxanes may also have cage structures of the formula R^(t)_(5m+α)R^(b) _(m-α)Al_(4m)O_(3m), wherein m is 3 or 4 and α is=n_(Al(3))−n_(O(2))+n_(O(4)); wherein n_(Al(3)) is the number of threecoordinate aluminum atoms, n_(O(2)) is the number of two coordinateoxygen atoms, n_(O(4)) is the number of 4 coordinate oxygen atoms, R^(t)represents a terminal alkyl group, and R^(b) represents a bridging alkylgroup; wherein R is a linear or branched alkyl having from 1 to 10carbon atoms.

In another aspect of this invention, the aluminoxanes that can be usedas an activator in this invention may be any combination of thealuminoxane compounds and structures presented herein.

Thus, aluminoxanes that may be used as activators in this invention aregenerally represented generally by formulas such as (R—Al—O)_(n),R(R—Al—O)_(n)AlR₂, and the like, wherein the R group is typically alinear or branched C₁-C₆ alkyl such as methyl, ethyl, propyl, butyl,pentyl, or hexyl wherein n typically represents an integer from 1 toabout 50. In one embodiment, the aluminoxane compounds of this inventioninclude, but are not limited to, methylaluminoxane, ethylaluminoxane,n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane,t-butyl-aluminoxane, sec-butylaluminoxane, iso-butylaluminoxane,1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane,iso-pentylaluminoxane, neopentylaluminoxane, or combinations thereof.

While organoaluminoxanes with different types of R groups areencompassed by the present invention, methyl aluminoxane (MAO), ethylaluminoxane, or isobutyl aluminoxane are typical activators used in thecatalyst compositions of this invention. These aluminoxanes are preparedfrom trimethylaluminum, triethylaluminum, or triisobutylaluminum,respectively, and are sometimes referred to as poly(methyl aluminumoxide), poly(ethyl aluminum oxide), and poly(isobutyl aluminum oxide),respectively. It is also within the scope of the invention to use analuminoxane in combination with a trialkylaluminum, such as disclosed inU.S. Pat. No. 4,794,096, which is incorporated herein by reference, inits entirety.

The present invention contemplates many values of n in the aluminoxaneformulas (R—Al—O)_(n) and R(R—Al—O)_(n)AlR₂, and preferably n is atleast about 3. However, depending upon how the organoaluminoxane isprepared, stored, and used, the value of n may be variable within asingle sample of aluminoxane, and such a combination oforganoaluminoxanes are comprised in the methods and compositions of thepresent invention.

Generally, any amount of the aluminoxane capable of activating thetransition metal compound may be utilized in this invention. Inpreparing the catalyst composition of this invention, the molar ratio ofthe aluminum in the aluminoxane to the transition metal compound in thecomposition is usually from about 1:1 to about 100,000:1. In one aspect,the molar ratio of the aluminum in the aluminoxane to the transitionmetal compound in the composition is from about 5:1 to about 15,000:1.In another aspect, the molar ratio of the aluminum in the aluminoxane tothe transition metal compound in the composition is usually from about5:1 to about 15,000:1. In yet another aspect, the amount of aluminoxaneadded to a polymerization zone is from about 0.01 mg/L to about 1000mg/L, and in another aspect, from about 0.1 mg/L to about 100 mg/L. Instill another aspect of this invention, the amount of aluminoxane usedmay be from about 1 mg/L to about 50 mg/L.

Organoaluminoxanes can be prepared by various procedures which are wellknown in the art. Examples of organoaluminoxane preparations aredisclosed in U.S. Pat. Nos. 3,242,099 and 4,808,561, each of which isincorporated herein by reference, in its entirety. One example of how analuminoxane may be prepared is as follows. Water which is dissolved inan inert organic solvent may be reacted with an aluminum alkyl compoundsuch as AlR₃ to form the desired organoaluminoxane compound. While notintending to be bound by this statement, it is believed that thissynthetic method can afford a mixture of both linear and cyclic(R—Al—O)_(n) aluminoxane species, both of which are encompassed by thisinvention. Alternatively, organoaluminoxanes may be prepared by reactingan aluminum alkyl compound such as AlR₃ with a hydrated salt, such ashydrated copper sulfate, in an inert organic solvent.

The aluminoxane activator may be supported or unsupported in the presentinvention. If supported, generally the support comprises an inorganicoxide, such as, silica, an aluminate compound, or combinations thereof.The use of a supported activator may result in a heterogeneous catalystcomposition, and an unsupported activator can result in a homogeneouscatalyst composition, and the present invention encompasses bothheterogeneous and homogeneous catalysts.

The Organoboron Activators

In accordance with this invention, the catalyst composition comprises atleast one transition metal compound and an activator. In one aspect ofthis invention, the activator comprises an organoboron compound. In oneaspect, the organoboron compound comprises neutral boron compounds,borate salts, or combinations thereof. For example, the organoboroncompounds of this invention can comprise a fluoroorgano boron compound,a fluoroorgano borate compound, or a combination thereof. Anyfluoroorgano boron or fluoroorgano borate compound known in the art canbe utilized. The term fluoroorgano boron compounds has its usual meaningto refer to neutral compounds of the form BY₃. The term fluoroorganoborate compound also has its usual meaning to refer to the monoanionicsalts of a fluoroorgano boron compound of the form [cation]⁺[BY₄]⁻,where Y represents a fluorinated organic group. For convenience,fluoroorgano boron and fluoroorgano borate compounds are typicallyreferred to collectively by organoboron compounds, or by either name asthe context requires.

Examples of fluoroorgano borate compounds that can be used ascocatalysts in the present invention include, but are not limited to,fluorinated aryl borates such as, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, lithiumtetrakis-(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbeniumtetrakis[3,5-bis(trifluoromethyl)-phenyl]borate, and the like, includingmixtures thereof. Examples of fluoroorgano boron compounds that can beused as cocatalysts in the present invention include, but are notlimited to, tris(pentafluorophenyl)boron,tris[3,5-bis(trifluoromethyl)-phenyl]boron, and the like, includingmixtures thereof.

Although not intending to be bound by the following theory, theseexamples of fluoroorgano borate and fluoroorgano boron compounds, andrelated compounds, are thought to form “weakly-coordinating” anions whencombined with organometal compounds, as disclosed in U.S. Pat. No.5,919,983, which is incorporated herein by reference in its entirety.

Generally, any amount of organoboron compound can be utilized in thisinvention. In one aspect, the molar ratio of the organoboron compound tothe transition metal compound in the composition is from about 0.1:1 toabout 10:1. In another aspect, the amount of the fluoroorgano boron orfluoroorgano borate compound used as a cocatalyst or activator for thetransition metal compound is in a range of from about 0.5 mole to about10 moles of boron compound per mole of transition metal compound. In oneaspect, the amount of fluoroorgano boron or fluoroorgano borate compoundused as a cocatalyst or activator for the transition metal compound isin a range of from about 0.8 mole to about 5 moles of boron compound permole of transition metal compound.

Like the aluminoxane activator, the fluoroorgano boron or fluoroorganoborate activators may be supported or unsupported in the presentinvention. If supported, generally the support comprises an inorganicoxide, such as, silica, an aluminate compound, or combinations thereof.The use of a supported activator may result in a heterogeneous catalystcomposition, and an unsupported activator can result in a homogeneouscatalyst composition, and the present invention encompasses bothheterogeneous and homogeneous catalysts.

The Ionizing Ionic Compound

In accordance with this invention, the catalyst composition comprises atleast one transition metal compound and an activator. In one aspect ofthis invention, the activator comprises at least one ionizing ioniccompound. Examples of ionizing ionic compound are disclosed in U.S. Pat.Nos. 5,576,259 and 5,807,938, each of which is incorporated herein byreference, in its entirety.

An ionizing ionic compound is an ionic compound which can function toactivate or enhance the activity of the catalyst composition. While notbound by theory, it is believed that the ionizing ionic compound may becapable of reacting with the transition metal compound and convertingthe transition metal compound into a cationic transition metal compound.Again, while not intending to be bound by theory, it is believed thatthe ionizing ionic compound may function as an ionizing compound bycompletely or partially extracting an anionic ligand, possibly a ligandsuch as (Z) or (Z′), from the transition metal compound. However, theionizing ionic compound is an activator regardless of whether it ionizesthe transition metal compound, abstracts a (Z) or (Z′) ligand in afashion as to form an ion pair, weakens the metal-(Z) or metal-(Z′) bondin the transition metal compound, simply coordinates to any ligand, orany other mechanisms by which activation may occur. Further, it is notnecessary that the ionizing ionic compound activate the transition metalcompound only. The activation function of the ionizing ionic compound isevident in the enhanced activity of catalyst composition as a whole, ascompared to a catalyst composition containing catalyst composition thatdoes not comprise any ionizing ionic compound.

Examples of ionizing ionic compounds include, but are not limited to,the following compounds: tri(n-butyl)ammonium tetrakis(p-tolyl)borate,tri(n-butyl)-ammonium tetrakis(m-tolyl)borate, tri(n-butyl)ammoniumtetrakis(2,4-dimethyl)-borate, tri(n-butyl)ammoniumtetrakis(3,5-dimethylphenyl)borate, tri(n-butyl)-ammoniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(p-tolyl)borate, N,N-dimethylanilinium tetrakis(m-tolyl)borate,N,N-dimethylanilinium tetrakis(2,4-dimethylphenyl)borate,N,N-dimethylanilinium tetrakis(3,5-dimethylphenyl)borate,N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate,N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,triphenylcarbenium tetrakis(p-tolyl)borate, triphenylcarbeniumtetrakis(m-tolyl)borate, triphenylcarbeniumtetrakis(2,4-dimethylphenyl)borate, triphenylcarbeniumtetrakis(3,5-dimethylphenyl)borate, triphenylcarbeniumtetrakis[3,5-bis(trifluoro-methyl)phenyl]borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, tropylium tetrakis(p-tolyl)borate,tropylium tetrakis(m-tolyl)borate, tropyliumtetrakis(2,4-dimethylphenyl)borate, tropyliumtetrakis(3,5-dimethylphenyl)borate, tropyliumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tropyliumtetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, lithium tetrakis(phenyl)borate,lithium tetrakis(p-tolyl)borate, lithium tetrakis(m-tolyl)borate,lithium tetrakis(2,4-dimethylphenyl)borate, lithiumtetrakis(3,5-dimethylphenyl)borate, lithium tetrafluoroborate, sodiumtetrakis(pentafluorophenyl)borate, sodium tetrakis(phenyl)borate, sodiumtetrakis(p-tolyl)borate, sodium tetrakis(m-tolyl)borate, sodiumtetrakis(2,4-dimethylphenyl)borate, sodiumtetrakis(3,5-dimethylphenyl)borate, sodium tetrafluoroborate, potassiumtetrakis-(pentafluorophenyl)borate, potassium tetrakis(phenyl)borate,potassium tetrakis(p-tolyl)borate, potassium tetrakis(m-tolyl)borate,potassium tetrakis(2,4-dimethylphenyl)borate, potassiumtetrakis(3,5-dimethylphenyl)borate, potassium tetrafluoroborate,tri(n-butyl)ammonium tetrakis(p-tolyl)aluminate, tri(n-butyl)ammoniumtetrakis(m-tolyl)aluminate, tri(n-butyl)ammoniumtetrakis(2,4-dimethyl)aluminate, tri(n-butyl)ammoniumtetrakis(3,5-dimethylphenyl)aluminate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)aluminate, N,N-dimethylaniliniumtetrakis(p-tolyl)aluminate, N,N-dimethylaniliniumtetrakis(m-tolyl)aluminate, N,N-dimethylaniliniumtetrakis(2,4-dimethylphenyl)aluminate, N,N-dimethylaniliniumtetrakis(3,5-dimethylphenyl)aluminate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)aluminate, triphenylcarbeniumtetrakis(p-tolyl)aluminate, triphenylcarbeniumtetrakis(m-tolyl)aluminate, triphenylcarbeniumtetrakis(2,4-dimethylphenyl)aluminate, triphenylcarbeniumtetrakis(3,5-dimethylphenyl)aluminate, triphenylcarbeniumtetrakis-(pentafluorophenyl)aluminate, tropyliumtetrakis(p-tolyl)aluminate, tropylium tetrakis(m-tolyl)aluminate,tropylium tetrakis(2,4-dimethylphenyl)aluminate, tropyliumtetrakis(3,5-dimethylphenyl)aluminate, tropyliumtetrakis(pentafluorophenyl)aluminate, lithiumtetrakis(pentafluorophenyl)aluminate, lithiumtetrakis-(phenyl)aluminate, lithium tetrakis(p-tolyl)aluminate, lithiumtetrakis(m-tolyl)aluminate, lithiumtetrakis(2,4-dimethylphenyl)aluminate, lithiumtetrakis(3,5-dimethylphenyl)aluminate, lithium tetrafluoroaluminate,sodium tetrakis(pentafluorophenyl)aluminate, sodiumtetrakis(phenyl)aluminate, sodium tetrakis(p-tolyl)aluminate, sodiumtetrakis(m-tolyl)aluminate, sodiumtetrakis(2,4-dimethylphenyl)aluminate, sodiumtetrakis(3,5-dimethylphenyl)aluminate, sodium tetrafluoroaluminate,potassium tetrakis(pentafluorophenyl)aluminate, potassiumtetrakis(phenyl)aluminate, potassium tetrakis(p-tolyl)aluminate,potassium tetrakis(m-tolyl)aluminate, potassiumtetrakis(2,4-dimethylphenyl)aluminate, potassiumtetrakis(3,5-dimethylphenyl)aluminate, potassium tetrafluoroaluminate,However, the ionizing ionic compound is not limited thereto in thepresent invention.

The Olefin Monomer

Unsaturated reactants that are useful in the polymerization processeswith catalyst compositions and processes of this invention includeolefin compounds having from about 2 to about 30 carbon atoms permolecule and having at least one olefinic double bond. This inventionencompasses homopolymerization processes using a single olefin such asethylene or propylene, as well as copolymerization reactions with atleast one different olefinic compound. In one aspect of acopolymerization reaction of ethylene, copolymers of ethylene comprise amajor amount of ethylene (>50 mole percent) and a minor amount ofcomonomer <50 mole percent), though this is not a requirement. Thecomonomers that can be copolymerized with ethylene should have fromthree to about 20 carbon atoms in their molecular chain.

Acyclic, cyclic, polycyclic, terminal (α), internal, linear, branched,substituted, unsubstituted, functionalized, and non-functionalizedolefins may be employed in this invention. For example, typicalunsaturated compounds that may be polymerized with the catalysts of thisinvention include, but are not limited to, propylene, 1-butene,2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene,3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-hexene,3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, the four normaloctenes, the four normal nonenes, the five normal decenes, and mixturesof any two or more thereof. Cyclic and bicyclic olefins, including butnot limited to, cyclopentene, cyclohexene, norbornylene, norbornadiene,and the like, may also be polymerized as described above.

In one aspect, when a copolymer is desired, the monomer ethylene may becopolymerized with a comonomer. In another aspect, examples of thecomonomer include, but are not limited to, propylene, 1-butene,2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene,3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-hexene,3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, the four normaloctenes, the four normal nonenes, or the five normal decenes. In anotheraspect, the comonomer may be 1-butene, 1-pentene, 1-hexene, 1-octene,1-decene, or styrene.

In one aspect, the amount of comonomer introduced into a reactor zone toproduce the copolymer is generally from about 0.01 to about 10 weightpercent comonomer based on the total weight of the monomer andcomonomer. In another aspect, the amount of comonomer introduced into areactor zone is from about 0.01 to about 5 weight percent comonomer, andin still another aspect, from about 0.1 to about 4 weight percentcomonomer based on the total weight of the monomer and comonomer.Alternatively, an amount sufficient to give the above describedconcentrations by weight, in the copolymer produced can be used.

While not intending to be bound by this theory, in the event thatbranched, substituted, or functionalized olefins are used as reactants,it is believed that steric hindrance may impede and/or slow thepolymerization process. Thus, branched and/or cyclic portion(s) of theolefin removed somewhat from the carbon-carbon double bond would not beexpected to hinder the reaction in the way that the same olefinsubstituents situated more proximate to the carbon-carbon double bondmight. In one aspect, at least one reactant for the catalystcompositions of this invention is ethylene, so the polymerizations areeither homopolymerizations or copolymerizations with a differentacyclic, cyclic, terminal, internal, linear, branched, substituted, orunsubstituted olefin. In addition, the catalyst compositions of thisinvention may be used in polymerization of diolefin compounds, includingbut not limited to, 1,3-butadiene, isoprene, 1,4-pentadiene, and1,5-hexadiene.

Preparation of the Catalyst Composition

In accordance with this invention, the catalyst compositions wereprepared by a process comprising contacting a transition metal compoundwith an activator. The contact process of preparing the catalyst of thisinvention may be carried out in an inert atmosphere and undersubstantially anhydrous conditions. In one aspect, the atmosphere issubstantially oxygen-free and substantially free of water as thereaction begins, to prevent deactivation of the catalyst. Thiscontacting procedure can occur in a variety of ways including, but notlimited to, blending or mixing. Further, each of the catalystcomposition components can be fed into the reactor separately, orvarious combinations of these compounds can be contacted together priorto being further contacted with additional catalyst components, or allcompounds can be contacted together before being introduced into thereactor.

In one aspect of this invention, the catalyst composition is prepared bycontacting the transition metal compound and the chemically-treatedsolid oxide component to form a first mixture, and then contacting thisfirst mixture with an organoaluminum compound to form a second mixturecomprising the catalyst composition. In the first mixture, thetransition metal compound and the chemically-treated solid oxidecomponent may be contacted from about 1 minute to about 24 hours at atemperature from about 10° C. to about 100° C. In another aspect, thetransition metal compound and the chemically-treated solid oxidecomponent may be contacted from about 1 minute to about 1 hour at atemperature from about 15° C. to about 50° C.

In another aspect of this invention, the catalyst composition isprepared by contacting the transition metal compound, the organoaluminumcompound, and the chemically-treated solid oxide component beforeinjection into a polymerization reactor. In this aspect, the transitionmetal compound, organoaluminum compound, and the chemically-treatedsolid oxide are contacted for a period from about 1 minute to about 24hours. In one aspect, this contact step occurs from about 1 minute toabout 1 hour, and at a temperature from about 10° C. to about 200° C. Inanother aspect, this contact step occurs at a temperature from about 20°C. to about 80° C.

Another aspect of this invention is contacting a transition metalcompound such as any of transition metal compounds A through R with anorganoaluminum compound such as Al(isobutyl)₃ for about 30 minutes toform a first mixture, prior to contacting this first mixture with achemically-treated solid oxide activator-support such as chloridedsilica-alumina to form a second mixture. Once the second mixture of allthe catalyst components is formed, it is optionally allowed to remain incontact from about 1 minute to about 24 hours prior to using this secondmixture in a polymerization process.

Another aspect of this invention is contacting a transition metalcompound such as any of transition metal compounds A through R with anorganoaluminum compound such as Al(isobutyl)₃ and with an α-olefinmonomer such as 1-hexene for about 30 minutes to form a first mixture,prior to contacting this first mixture with an acidic activator-supportsuch as chlorided alumina to form a second mixture. Once the secondmixture of all the catalyst components is formed, it is optionallyallowed to remain in contact from about 1 minute to about 24 hours priorto using this second mixture in a polymerization process.

In one aspect, the weight ratio of the organoaluminum compound to thetreated solid oxide component in the catalyst composition may be fromabout 5:1 to about 1:1000. In another aspect, the weight ratio of theorganoaluminum compound to the treated solid oxide component in thecatalyst composition may be from about 3:1 to about 1:100, and inanother aspect, from about 1:1 to about 1:50. These weight ratios arebased on the combined weights of organoaluminum, treated oxide, andtransition metal compound used to prepare the catalyst composition,regardless of the order of contacting the catalyst components.

In another aspect, the weight ratio of the treated solid oxide componentto the transition metal compound in the catalyst composition may be fromabout 10,000:1 to about 1:1. In another aspect, the weight ratio of thetreated solid oxide component to the transition metal compound in thecatalyst composition may be from about 1000:1 to about 10:1, and in yetanother aspect, from about 250:1 to about 20:1. These weight ratios arebased on the combined weights of organoaluminum, treated oxide, andtransition metal compound used to prepare the catalyst composition,regardless of the order of contacting the catalyst components.

Utility of the Catalyst Composition in Polymerization Processes

Polymerizations using the catalysts of this invention can be carried outin any manner known in the art. Such polymerization processes include,but are not limited to slurry polymerizations, gas phasepolymerizations, solution polymerizations, and the like, includingmulti-reactor combinations thereof. Thus, any polymerization zone knownin the art to produce ethylene-containing polymers can be utilized. Forexample, a stirred reactor can be utilized for a batch process, or thereaction can be carried out continuously in a loop reactor or in acontinuous stirred reactor.

After catalyst activation, a catalyst composition is used tohomopolymerize ethylene, or copolymerize ethylene with a comonomer. Inone aspect, a typical polymerization method is a slurry polymerizationprocess (also known as the particle form process), which is well knownin the art and is disclosed, for example in U.S. Pat. No. 3,248,179,which is incorporated by reference herein, in its entirety. Otherpolymerization methods of the present invention for slurry processes arethose employing a loop reactor of the type disclosed in U.S. Pat. No.6,239,235 which is also incorporated by reference herein, in itsentirety.

In one aspect, polymerization temperature for this invention may rangefrom about 60° C. to about 280° C., and in another aspect,polymerization reaction temperature may range from about 70° C. to about110° C.

The polymerization reaction typically occurs in an inert atmosphere,that is, in atmosphere substantial free of oxygen and undersubstantially anhydrous conditions, thus, in the absence of water as thereaction begins. Therefore a dry, inert atmosphere, for example, drynitrogen or dry argon, is typically employed in the polymerizationreactor.

The polymerization reaction pressure can be any pressure that does notadversely affect the polymerization reaction, and it typically conductedat a pressure higher than the pretreatment pressures. In one aspect,polymerization pressures may be from about atmospheric pressure to about1000 psig. In another aspect, polymerization pressures may be from about50 psig to about 800 psig. Further, hydrogen can be used in thepolymerization process of this invention to control polymer molecularweight.

Polymerizations using the catalysts of this invention can be carried outin any manner known in the art. Such processes that can polymerizemonomers into polymers include, but are not limited to slurrypolymerizations, gas phase polymerizations, solution polymerizations,and multi-reactor combinations thereof. Thus, any polymerization zoneknown in the art to produce olefin-containing polymers can be utilized.For example, a stirred reactor can be utilized for a batch process, orthe reaction can be carried out continuously in a loop reactor or in acontinuous stirred reactor. Typically, the polymerizations disclosedherein are carried out using a slurry polymerization process in a loopreaction zone. Suitable diluents used in slurry polymerization are wellknown in the art and include hydrocarbons which are liquid underreaction conditions. The term “diluent” as used in this disclosure doesnot necessarily mean an inert material, as this term is meant to includecompounds and compositions that may contribute to polymerizationprocess. Examples of hydrocarbons that can be used as diluents include,but are not limited to, cyclohexane, isobutane, n-butane, propane,n-pentane, isopentane, neopentane, and n-hexane. Typically, isobutane isused as the diluent in a slurry polymerization. Examples of thistechnology are found in U.S. Pat. Nos. 4,424,341; 4,501,885; 4,613,484;4,737,280; and 5,597,892; each of which is incorporated by referenceherein, in its entirety.

For purposes of the invention, the term polymerization reactor includesany polymerization reactor or polymerization reactor system known in theart that is capable of polymerizing olefin monomers to producehomopolymers or copolymers of the present invention. Such reactors cancomprise slurry reactors, gas-phase reactors, solution reactors, or anycombination thereof. Gas phase reactors can comprise fluidized bedreactors or tubular reactors. Slurry reactors can comprise verticalloops or horizontal loops. Solution reactors can comprise stirred tankor autoclave reactors.

Polymerization reactors suitable for the present invention can compriseat least one raw material feed system, at least one feed system forcatalyst or catalyst components, at least one reactor system, at leastone polymer recovery system or any suitable combination thereof.Suitable reactors for the present invention can further comprise anyone, or combination of, a catalyst storage system, an extrusion system,a cooling system, a diluent recycling system, or a control system. Suchreactors can comprise continuous take-off and direct recycling ofcatalyst, diluent, and polymer. Generally, continuous processes cancomprise the continuous introduction of a monomer, a catalyst, and adiluent into a polymerization reactor and the continuous removal fromthis reactor of a suspension comprising polymer particles and thediluent.

Polymerization reactor systems of the present invention can comprise onetype of reactor per system or multiple reactor systems comprising two ormore types of reactors operated in parallel or in series. Multiplereactor systems can comprise reactors connected together to performpolymerization, or reactors that are not connected. The polymer can bepolymerized in one reactor under one set of conditions, and then thepolymer can be transferred to a second reactor for polymerization undera different set of conditions.

In one aspect of the invention, the polymerization reactor system cancomprise at least one loop slurry reactor. Such reactors are known inthe art and can comprise vertical or horizontal loops. Such loops cancomprise a single loop or a series of loops. Multiple loop reactors cancomprise both vertical and horizontal loops. The slurry polymerizationcan be performed in an organic solvent that can disperse the catalystand polymer. Examples of suitable solvents include butane, hexane,cyclohexane, octane, and isobutane. Monomer, solvent, catalyst and anycomonomer are continuously fed to a loop reactor where polymerizationoccurs. Polymerization can occur at low temperatures and pressures.Reactor effluent can be flashed to remove the solid resin.

In yet another aspect of this invention, the polymerization reactor cancomprise at least one gas phase reactor. Such systems can employ acontinuous recycle stream containing one or more monomers continuouslycycled through the fluidized bed in the presence of the catalyst underpolymerization conditions. The recycle stream can be withdrawn from thefluidized bed and recycled back into the reactor. Simultaneously,polymer product can be withdrawn from the reactor and new or freshmonomer can be added to replace the polymerized monomer. Such gas phasereactors can comprise a process for multi-step gas-phase polymerizationof olefins, in which olefins are polymerized in the gaseous phase in atleast two independent gas-phase polymerization zones while feeding acatalyst-containing polymer formed in a first polymerization zone to asecond polymerization zone.

In still another aspect of the invention, the polymerization reactor cancomprise a tubular reactor. Tubular reactors can make polymers by freeradical initiation, or by employing the catalysts typically used forcoordination polymerization. Tubular reactors can have several zoneswhere fresh monomer, initiators, or catalysts are added. Monomer can beentrained in an inert gaseous stream and introduced at one zone of thereactor. Initiators, catalysts, and/or catalyst components can beentrained in a gaseous stream and introduced at another zone of thereactor. The gas streams are intermixed for polymerization. Heat andpressure can be employed appropriately to obtain optimal polymerizationreaction conditions.

In another aspect of the invention, the polymerization reactor cancomprise a solution polymerization reactor. During solutionpolymerization, the monomer is contacted with the catalyst compositionby suitable stirring or other means. A carrier comprising an inertorganic diluent or excess monomer can be employed. If desired, themonomer can be brought in the vapor phase into contact with thecatalytic reaction product, in the presence or absence of liquidmaterial. The polymerization zone is maintained at temperatures andpressures that will result in the formation of a solution of the polymerin a reaction medium. Agitation can be employed during polymerization toobtain better temperature control and to maintain uniform polymerizationmixtures throughout the polymerization zone. Adequate means are utilizedfor dissipating the exothermic heat of polymerization. Thepolymerization can be effected in a batch manner, or in a continuousmanner. The reactor can comprise a series of at least one separator thatemploys high pressure and low pressure to separate the desired polymer.

In a further aspect of the invention, the polymerization reactor systemcan comprise the combination of two or more reactors. Production ofpolymers in multiple reactors can include several stages in at least twoseparate polymerization reactors interconnected by a transfer devicemaking it possible to transfer the polymers resulting from the firstpolymerization reactor into the second reactor. The desiredpolymerization conditions in one of the reactors can be different fromthe operating conditions of the other reactors. Alternatively,polymerization in multiple reactors can include the manual transfer ofpolymer from one reactor to subsequent reactors for continuedpolymerization. Such reactors can include any combination including, butnot limited to, multiple loop reactors, multiple gas reactors, acombination of loop and gas reactors, a combination of autoclavereactors or solution reactors with gas or loop reactors, multiplesolution reactors, or multiple autoclave reactors.

After the polymers are produced, they can be formed into variousarticles, including but not limited to, household containers, utensils,film products, drums, fuel tanks, pipes, geomembranes, and liners.Various processes can form these articles. Usually, additives andmodifiers are added to the polymer in order to provide desired effects.By using the invention described herein, articles can likely be producedat a lower cost, while maintaining most or all of the unique propertiesof polymers produced with transition metal compound catalysts.

Definitions

In order to more clearly define the terms used herein, the followingdefinitions are provided. To the extent that any definition or usageprovided by any document incorporated herein by reference conflicts withthe definition or usage provided herein, the definition or usageprovided herein controls.

The term polymer is used herein to mean homopolymers comprising ethyleneand/or copolymers of ethylene and another olefinic comonomer. Polymer isalso used herein to mean homopolymers and copolymers of acetylenes.

The term inert atmosphere is used herein to refer to any type of ambientatmosphere that is substantially unreactive toward the particularreaction, process, or material around which the atmosphere surrounds orblankets. Thus, this term is typically used herein to refer to the useof a substantially oxygen-free and moisture-free blanketing gas,including but not limited to dry argon, dry nitrogen, dry helium, ormixtures thereof, when any precursor, component, intermediate, orproduct of a reaction or process is sensitive to particular gases ormoisture. Additionally, inert atmosphere is also used herein to refer tothe use of dry air as a blanketing atmosphere when the precursors,components, intermediates, or products of the reaction or process areonly moisture-sensitive and not oxygen-sensitive. However, inertatmosphere, as used herein, would typically exclude CO₂ or CO becausethese gases may be reactive toward the particular reaction, process, ormaterial around which they would surround or blanket, despite theiroccasional use as inert blanketing gases in other processes.

The terms catalyst composition, catalyst mixture, and the like are usedherein to refer to the mixture of catalyst components disclosed herein,regardless of the actual product of the reaction of the components, thenature of the active catalytic site, or the fate of any one componentsuch as organometal compound and activator. Therefore, the termscatalyst composition, catalyst mixture, and the like include bothheterogeneous compositions and homogenous compositions.

The term hydrocarbyl is used to specify a hydrocarbon radical group thatincludes, but is not limited to aryl, alkyl, cycloalkyl, alkenyl,cycloalkenyl, cycloalkadienyl, alkynyl, aralkyl, aralkenyl, aralkynyl,and the like, and includes all substituted, unsubstituted, branched,linear, heteroatom substituted derivatives thereof.

The terms activator, cocatalyst, and related terms are genericdescriptors used to refer to the compounds, compositions, or mixturesthat are contacted with the transition metal compounds to form thecatalyst compositions of this invention, regardless of any particularreaction or mechanism by which such compounds, compositions, or mixturesfunction. Activators include, but are not limited to: compounds such asan aluminoxane, an organoboron compound, an ionizing ionic compound, aclay material, a chemically-treated solid oxide, or any combinationthereof. In another aspect, the term activator is used to refer tocompositions or mixtures, examples of which include, but are not limitedto, mixtures of chemically-treated solid oxides and organoaluminumcompounds, and mixtures of clays or other layered materials andorganoaluminum compounds.

The term chemically-treated solid oxide is used interchangeably withterms such as solid acidic activator-support, acidic activator-support,or simply activator-support, and the like to indicate achemically-treated, solid, inorganic oxide of relatively high porosity,which exhibits enhanced Lewis acidic or Brønsted acidic behavior,arising through treatment of the solid oxide with anelectron-withdrawing component, typically an electron-withdrawing anionor an electron-withdrawing anion source compound. These terms are notused to imply this component is inert, and it should not be construed asan inert component of the catalyst composition. Rather, thechemically-treated solid oxides in combination with the organoaluminumcompounds comprise activators of the transition metal compounds andcomprise an insoluble component of the catalyst composition of thisinvention to produce polymers, and at which the active catalytic sitesare situated, and are not intended to be limiting.

Although any methods, devices, and materials similar or equivalent tothose described herein can be used in the practice or testing of theinvention, the typical methods, devices and materials are hereindescribed.

All publications and patents mentioned herein are incorporated herein byreference for the purpose of describing and disclosing, for example, theconstructs and methodologies that are described in the publications,which might be used in connection with the presently describedinvention. The publications discussed above and throughout the text areprovided solely for their disclosure prior to the filing date of thepresent application. Nothing herein is to be construed as an admissionthat the inventors are not entitled to antedate such disclosure byvirtue of prior invention.

For any particular compound disclosed herein, any general structurepresented also encompasses all conformational isomers, regioisomers, andstereoisomers that may arise from a particular set of substituents. Thegeneral structure also encompasses all enantiomers, diastereomers, andother optical isomers whether in enantiomeric or racemic forms, as wellas mixtures of stereoisomers, as the context requires.

The present invention is further illustrated by the following examples,which are not to be construed in any way as imposing limitations uponthe scope thereof. On the contrary, it is to be clearly understood thatresort may be had to various other aspects, embodiments, modifications,and equivalents thereof which, after reading the description herein, maysuggest themselves to one of ordinary skill in the art without departingfrom the spirit of the present invention or the scope of the appendedclaims.

In the following examples, unless otherwise specified, the syntheses andpreparations described therein were carried out under an inertatmosphere such as nitrogen and/or argon. Solvents were purchased fromcommercial sources and were typically dried over activated alumina priorto use, or distilled from potassium metal prior to use. Unless otherwisespecified, reagents were obtained from commercial sources.

EXAMPLE 1 Testing Methods

A “Quantachrome Autosorb-6 Nitrogen Pore Size Distribution Instrument,”acquired from the Quantachrome Corporation, Syosset, N.Y., was used todetermine surface areas and pore volumes of the treated oxideactivator-supports of this invention. The Melt Index (MI) of the polymerproduct was determined using a 2.16 kg load and High Load Melt Index(HLMI) was determined with a 21.6 kg load at 190° C. according to ASTMD-1238. Polymer density was determined in grams per cubic centimeter(g/cc) on a compression molded sample, cooled at about 15° C. per hour,and conditioned for about 40 hours at room temperature in accordancewith ASTM D1505 and ASTM D1928, procedure C.

Molecular weights and molecular weight distributions were obtained usinga PL 220 SEC high temperature chromatography unit (Polymer Laboratories)with trichlorobenzene (TCB) as the solvent, with a flow rate of 1mL/minute at a temperature of 145° C. BHT(2,6-di-tert-butyl-4-methylphenol) at a concentration of 0.5 g/L wasused as a stabilizer in the TCB. An injection volume of 200 μL was usedwith a nominal polymer concentration of 1.5 mg/mL. Dissolution of thesample in stabilized TCB was carried out by heating at 150° C. for 5hours with occasional, gentle agitation. The columns used were threeMixed A LS columns (7.8×300 mm) and were calibrated with a broad linearpolyethylene standard (Chevron Phillips Marlex® BHB 5003) for which themolecular weight had been determined.

The comonomer content of polyethylene can be determined using carbon-13nuclear magnetic resonance (NMR) spectroscopy. A sample of polyethyleneis placed in a high boiling solvent, typically 1,2,4-trichlorobenzene.This mixture is heated above the dissolution temperature of thepolyethylene sample, between 130 to 160 degrees Celsius, obtaining ahomogeneous solution. This solution is placed in an NMR spectrometer andthe C-13 spectrum obtained under conditions that produce a spectrum witha quantitative signal for each type of carbon atom in the mixture. Theseconditions include heating the sample above the dissolution temperatureto maintain a homogeneous solution, complete decoupling, and relaxationdelays greater than five times the longest spin lattice relaxation time(Each carbon atom has a spin-lattice relaxation time, which is measuredindependently to determine the relaxation delays).

Typical conditions are Waltz-16 decoupling on the hydrogen channel, arelaxation delay of 10 seconds, a pulse width of 90 degrees, and asample temperature of 125 degrees Celsius. The carbon atoms associatedwith the incorporated comonomer are distinct from those carbon atomsassociated with incorporated ethylene. By integrating the signals fromthe carbons from the integrated comonomer and the signals from thecarbons associated with ethylene, one obtains two numbers, Nc and Ne,e.g. an non-normalized number representing the number of carbon atomsfrom comonomer and a non-normalized number representing the number ofcarbon atoms from ethylene. Correcting these numbers (Nc & Ne) for thenumber of moles/carbon atoms and subsequent normalization will producethe mole percent comonomer in the resin. The comonomer contentdetermination was performed utilizing a Varian Inova 500 spectrometeroperating at 125 MHz for 13 C.

EXAMPLE 2

The transition metal compounds were prepared according to standardmethods as disclosed in: Grochall, L., Stahl, L., Staples, R. J., J.Chem. Soc., Chem. Commun. 1997, 1465; Okuda, J., Fokken, S., Kang, H.,Massa, W., Chem. Ber. 1995, 128, 221; van der Linden, A., Schaverien, C.J., Meijboom, N., Ganter, C., Orpen, A. G., J. Am. Chem. Soc. 1995,117(11), 3008; Doherty, S., Errington, R. J., Houssley, N., Ridland, J.,Clegg, W., Elsegood, M. R. J., Organometallics, 1999, 18(6), 1018;Tshuva, E. Y., Goldberg, I., Kol, M., J. Am. Chem. Soc. 2000, 122(43),10706; Schrock, R. R., Casado, A. L., Goodman, J. T., Liang, L.,Bonitatebus Jr, P. J., Davis, W. M., Organometallics, 2000, 19, 5325;Jensen, M. J., Farmer, K. R., U.S. Pat. No. 6,380,329; and Gibson, V.C., Spitzmesser, S. K., Chem. Rev. 2003, 103, 283-315

EXAMPLE 3 General Sources and Properties of the Solid Oxide MaterialsUsed to Prepare the Treated Solid Oxides

Alumina was obtained as Ketjen™ grade B from Akzo Nobel, having a porevolume of about 1.78 cc/g and a surface area of about 340 m²/g orKetjen™ L 95-98% alumina and 2-5% silica having a pore volume of 2.00cc/g and surface area of 380 m²/g. Silica was obtained as Davison grade952 from W.R. Grace, having a pore volume of about 1.6 cc/g and asurface area of about 300 m²/g. Silica-alumina was obtained as MS13-110from W.R. Grace having 13% by weight alumina and 87% by weight silicaand having a pore volume of about 1.2 cc/g and a surface area of about350 m²/g.

EXAMPLE 4 Preparation of Sulfated Alumina Activator-Support

Ketjen™ L alumina, 652 g, was impregnated to just beyond incipientwetness with a solution containing 137 g of (NH₄)₂SO₄ dissolved in 1300mL of water. This mixture was then placed in a vacuum oven and driedovernight at 110° C. under half an atmosphere of vacuum and thencalcined in a muffle furnace at 300° C. for 3 hours, then at 450° C. for3 hours, after which the resulting activated support was screenedthrough an 80 mesh screen, and subsequently activated in air at 550° C.for 6 hours, after which the resulting treated solid oxide activatorsupport was stored under nitrogen until used.

EXAMPLE 5 Preparation of a Chlorided Alumina Activator-Support

Ten mL of Ketjen™ Grade B alumina was calcined in air for three hours at600° C. After this calcining step, the furnace temperature was loweredto about 400° C., and a nitrogen stream was initiated over the aluminabed, after which 1.0 mL of carbon tetrachloride was injected into thenitrogen stream and evaporated upstream from the alumina bed. This gasphase CCl₄ was carried into the bed and there reacted with the aluminato chloride the surface. This process provided the equivalent to about15.5 mmol of chloride ion per gram of dehydrated alumina. After thischloriding treatment, the resulting alumina was white in color. Thistreated solid oxide activator support was used in the same manner as thesulfated alumina.

EXAMPLE 6 Preparation of Fluorided Silica-Alumina Activator-Support

Silica-alumina, MS13-110 from W.R. Grace Company, 700 g, was impregnatedto just beyond incipient wetness with a solution containing 70 g ofammonium bifluoride dissolved in 1250 mL of water. This mixture was thenplaced in a vacuum oven and dried overnight at 120° C. under half anatmosphere of vacuum. The final step in producing activated-support wasto calcine the material in dry fluidizing air at 454° C. for 6 hours,after which the treated solid oxide activator support was stored undernitrogen until used.

EXAMPLE 7 General Description of the Polymerization Runs

Polymerizations were carried out in a 1 gallon Autoclave Engineersstirrer reactor, fitted with an oil-less packing with a flat stirrerrunning at 700 rpm. The reactor temperature was regulated by controllingthe temperature of the water in the steel jacket using steam and waterheat exchangers, with electronic instrumentation to control flows.Catalysts were added while the autoclave temperature was below 40° C.under a purge of isobutane. The autoclave was then sealed and 2 L ofisobutane were added and stirring started at 700 rpm. Reactor heatingwas then initiated and as the reactor temperature approached 60° C.,ethylene addition was initiated. The hexene was flushed in with theethylene from an in-line vessel on top of the reactor. The set pointtemperature and pressure were then rapidly attained. The reactor washeld under these conditions for 60 minutes by feeding ethylene ondemand. The polymerization was then terminated by venting the volatilesto the flare system. This process left the polyethylene as a wet solidin the reactor, which was collected, and the solid air dried to yieldgranular polyethylene.

EXAMPLE 8 Polymerization using bis(tert-butylamido)cyclodiphosphazanezirconium dibenzyl (A)

For each run, to a 1 gallon Autoclave Engineers stirred reactor wasadded 30 mg of the transition metal complex A and 300 mg of the sulfatedalumina from Example 4. The autoclave was sealed and 2 L of isobutanewas added and stirring started at 700 rpm. The reactor heating was theninitiated. As the reactor approached 60° C., ethylene (and 1-hexene, ifused) was added. The reactor was held at set point for 60 minutes byfeeding ethylene on demand. The polymerization was terminated by ventingthe volatiles to the flare system. This procedure left the polyethyleneas a wet solid in the reactor. The polyethylene solid was then airdried. The results are summarized in Table 1. TABLE 1 Run Catalyst AActivator 1-hexene Polymer MI HLMI Density No. (mg) (mg) (gm) (gm)(gm/10 min) (gm/10 min) (gm/cc) 1 30 300 0 29 0 0 0.9354 2 30 300 20 100 0 0.9432Run No. 1 was at 90° C., 550 psig ethyleneRun No. 2 was at 80° C., 550 psig ethylene

EXAMPLE 9 Polymerization Process Usingbis(tert-butylamido)cyclodiphosphazane zirconium dichloride (B)

To a 1 gallon Autoclave Engineers stirred reactor was added 20 mg of thetransition metal complex B, 300 mg of the sulfated alumina from Example4, and 1 mL of a 25 wt % heptane solution of triisobutylaluminum (TIBAL)as a co-catalyst. The autoclave was sealed and 2 L of isobutane wereadded and stirring started at 700 rpm. The reactor heating was theninitiated. As the reactor approached 60° C., ethylene addition wasbegun. The set point of 80° C. and 550 psig was then rapidly attained.The reactor was held at set point for 60 minutes by feeding ethylene ondemand. The polymerization was terminated by venting the volatiles tothe flare system. This procedure left the polyethylene as a wet solid inthe reactor. The polyethylene solid was then air dried. The results aresummarized in Table 2. TABLE 2 Run Catalyst B Activator Co-catalystPolymer MI HLMI Density No. (mg) (mg) (ml) (g) (gm/10 min) (gm/10 min)(gm/cc) 3 20 300 1 9 0 0 N/DN/D is not determined

EXAMPLE 10 Polymerization Process Using2,2′-methylenebis(6-tert-butyl-4-methylphenoxy)titanium dichloride (C)

For each run, to a 1 gallon Autoclave Engineers stirred reactor wasadded 20 mg of the transition metal complex C and 300 mg of the sulfatedalumina from Example 4, and 1 mL of a 25 wt % heptane solution oftriisobutylaluminum. The autoclave was sealed and 2 L of isobutane wasadded and stirring started at 700 rpm. The reactor heating was theninitiated. As the reactor approached 60° C., ethylene (and 1-hexene, ifused) was added. The set point of 80° C. and 550 psig was then rapidlyattained. The reactor was held at set point for 60 minutes by feedingethylene on demand. The polymerization was terminated by venting thevolatiles to the flare system. This procedure left the polyethylene as awet solid in the reactor. The polyethylene solid was then air dried. Theresults are summarized in Table 3. TABLE 3 1- Run Catalyst C Co-catalysthexene Polymer MI HLMI Density No. (mg) Activator (mg) (ml) (gm) (gm)(gm/10 min) (gm/10 min) (gm/cc) 4 20 300 1 20 43 0 0 N/D 5 20 300 1 0 690 0 0.9372

EXAMPLE 11 Polymerization Process Using2,2′-thiobis(6-tert-butyl-4-methylphenoxy)titanium dichloride (D)

For each run, to a 1 gallon Autoclave Engineers stirred reactor wasadded 15 mg of the transition metal complex D and 250 mg ofactivator/support, and 1 mL of a 25 wt % heptane solution oftriisobutylaluminum. The autoclave was sealed and 2 L of isobutane wasadded and stirring started at 700 rpm. The reactor heating was theninitiated. As the reactor approached 60° C., ethylene (and 1-hexene, ifused) were added. The reactor was held at set point for 60 minutes byfeeding ethylene on demand. The polymerization was terminated by ventingthe volatiles to the flare system. This procedure left the polyethyleneas a wet solid in the reactor. The polyethylene solid was air dried. Theresults are summarized in Table 4. TABLE 4 Co- 1- Run Catalyst DActivator Activator catalyst hexene Polymer MI HLMI No. (mg) Type (mg)(ml) (gm) (gm) (gm/10 min) (gm/10 min) 6 15 Cl—Al 250 1 0 27 0 0 7 15S—Al 250 1 20 13 0 0Cl—Al is chlorided aluminaS—Al is sulfated aluminaRun 6 at 80° C. and 450 psig ethyleneRun 7 at 90° C. and 450 psig ethylene

EXAMPLE 12 Polymerization Process Using N-alkoxy-β-ketoiminatetetrahydrofuran titanium dichloride (E)

To a 1 gallon Autoclave Engineers stirred reactor was added 20 mg of thetransition metal complex E, 300 mg of the sulfated alumina from Example4, and 1 mL of a 25 wt % heptane solution of triisobutylaluminum. Theautoclave was sealed and 2 L of isobutane was added and stirring startedat 700 rpm. The reactor heating was then initiated. As the reactorapproached 60° C., ethylene addition was begun. The set point of 80° C.and 550 psig was then rapidly attained. The reactor was held at setpoint for 60 minutes by feeding ethylene on demand. The polymerizationwas terminated by venting the volatiles to the flare system. Thisprocedure left the polyethylene as a wet solid in the reactor. Thepolyethylene solid was air dried. The results are summarized in Table 5.TABLE 5 Run Catalyst E Activator Activator Co-catalyst Polymer MI HLMIDensity No. (mg) Type (mg) (ml) (g) (gm/10 min) (gm/10 min) (gm/cc) 8 20S—Al 300 1 14 0 0 0.9453

EXAMPLE 13 Polymerization Process Using 2,2′-[1,2ethanebis[methylamido-N]methylene]bis[4,6 tert-butylphenoxy]zirconiumdibenzyl (F)

To a 1 gallon Autoclave Engineers stirred reactor was added 10 mg of thetransition metal complex F, 200 mg of the sulfated alumina from Example4, and 1 mL of a 25 wt % heptane solution of triisobutylaluminum. Theautoclave was sealed and 2 L of isobutane was added and stirring startedat 700 rpm. The reactor heating was then initiated. As the reactorapproached 60° C., ethylene addition was begun. The set point of 80° C.and 550 psig was then rapidly attained. The reactor was held at setpoint for 60 minutes by feeding ethylene on demand. The polymerizationwas terminated by venting the volatiles to the flare system. Thisprocedure left the polyethylene as a wet solid in the reactor. Thepolyethylene solid was air dried. The results are summarized in Table 6.TABLE 6 Activator Co- Run Catalyst F Activator amount catalyst PolymerMI HLMI Density No. (mg) Type (mg) (ml) (g) (gm/10 min) (gm/10 min)(gm/cc) 9 10 S—Al 200 1 12 0 0 0.9428

EXAMPLE 14 Polymerization Process UsingN,N′-[(amino-N)di-2,1-ethane]bis[2-N-2,4,6 trimethylphenylamido]zirconium dibenzyl (G)

For each run, to a 1 gallon Autoclave Engineers stirred reactor wasadded the transition metal complex G and either sulfated alumina fromExample 4 or fluorided silica-alumina from Example 6. The autoclave wassealed and 2 L of isobutane was added and stirring started at 700 rpm.The reactor heating was then initiated. As the reactor approached 60°C., ethylene addition was begun. The set point of 80° C. and 550 psigwas then rapidly attained. The reactor was held at set point for 60minutes by feeding ethylene on demand. The polymerization was terminatedby venting the volatiles to the flare system. This procedure left thepolyethylene as a wet solid in the reactor. The polyethylene solid wasair dried. The results are summarized in Table 7. TABLE 7 Activator Co-Run Catalyst G Activator amount catalyst Polymer MI HLMI Density No.(mg) Type (mg) (ml) (g) (gm/10 min) (gm/10 min) (gm/cc) 10 10 S—AL 100 1ml 427 0 0 11 20 S—AL 300 288 0 0 0.9627 12 25 F—SiAl 400 1 ml 118 0 013 25 F—SiAl 400 43 0 0 0.9345

EXAMPLE 15 Comparison of Inventive Catalysts and Aluminoxane Catalysts

As a comparison, the polymerization of the inventive catalystcompositions was compared to similar catalysts employingmethylaluminoxane as a co-catalyst.

For each run, to a 1 gallon Autoclave Engineers stirred reactor wasadded the indicated amount of the transition metal complex G. For runs15 and 17, 100 mg of sulfated alumina from Example 4 was used as theactivator, and 1 mL of a 25 wt % solution of triisobutylaluminum wasused as a co-catalyst. For runs 14 and 16, 3 mL of a 10 wt % toluenesolution of methylaluminoxane (MAO) was used as the activator. Theautoclave was sealed and 2 L of isobutane was added and stirring startedat 700 rpm. The reactor heating was then initiated. As the reactorapproached 60° C., ethylene addition was begun. The reactor was held at80° C. and 450 psig pressure for the indicated time by feeding ethyleneon demand. The polymerization was terminated by venting the volatiles tothe flare system. This procedure left the polyethylene as a wet solid inthe reactor. The polyethylene solid was air dried. The results aresummarized in Table 8. TABLE 8 Co- Co- Run Catalyst G ActivatorActivator catalyst 1-hexene Polymer Monomer Mw/ Mn/ Mw/ Density No. (mg)Type amount (ml) (gm) (g) (mole %) 1000 1000 Mn (gm/cc) 14 5 MAO 3 ml 40136 0.14 1196 266 4.5 0.9307 15 10 S—Al 100 mg 1 ml 40 196 0.22 2164 5034.3 0.9216 16 5 MAO 3 ml 30 111 0.12 0.931 17 10 S—Al 100 mg 1 ml 30 1430.39 0.9222MAO is a 10 wt % toluene solution of methylaluminoxane received fromWitco.Runs 14 and 16 were for 30 minutes, runs 15 and 17 were for 60 minutes

As shown in Table 8, the inventive catalyst run 15, comprisingtransition metal catalyst compound G, triisobutylaluminum and sulfatedalumina shows higher comonomer incorporation and yields higher molecularweight polymers than the more expensive methylaluminoxane/transitionmetal catalyst compound G catalyst system.

1. A catalyst composition comprising: a) a transition metal compoundwith the following formula:

wherein: M is titanium, zirconium, or hafnium; R_(n) is an alkyl, aryl,alkaryl or arylaryl group containing 1-20 carbon atoms; n is 0 or 1; Xis independently a group 15 or group 16 element; E is a divalentbridging group containing up to 40 atoms, not counting hydrogen, whichlinks X and Y; Y is independently a group 15 or group 16 element; a is1, 2, 3, or 4; Z is a monovalent anionic group; Z′ is a monovalentanionic group; b is 0, 1 or 2, and c is 0, 1 or 2; L is a neutral donorligand; d is 0, 1 or 2; and b) a chemically-treated solid oxide.
 2. Thecatalyst composition according to claim 1 wherein X is nitrogen, oxygen,phosphorus or sulfur.
 3. The catalyst composition according to claim 1wherein Y is nitrogen, oxygen, phosphorus or sulfur.
 4. The catalystcomposition according to claim 1 wherein (Z) and (Z′) are independentlyan aliphatic group, an aromatic group, a cyclic group, a combination ofaliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogengroup, a phosphorus group, an arsenic group, a carbon group, a silicongroup, a germanium group, a tin group, a lead group, a boron group, analuminum group, an inorganic group, an organometallic group, or asubstituted derivative thereof, any one of which having from 1 to about20 carbon atoms; or a halide.
 5. The catalyst composition of claim 1wherein the chemically-treated solid oxide comprises a solid oxidetreated with an electron-withdrawing anion.
 6. The catalyst compositionof claim 5 wherein the solid oxide is silica, alumina, silica-alumina,aluminum phosphate, heteropolytungstates, a clay, titania, zirconia,magnesia, boria, zinc oxide, mixed oxides thereof, or mixtures thereof.7. The catalyst composition of claim 5 wherein the electron-withdrawinganion is fluoride, chloride, bromide, phosphate, triflate, bisulfate,sulfate, or any combination thereof.
 8. The catalyst composition ofclaim 1 wherein L is selected from ethers, furans and nitriles.
 9. Thecatalyst composition of claim 1 further comprising an aluminoxane, anorganoboron compound, an ionizing ionic compound, or any combinationthereof.
 10. The catalyst composition of claim 1 further comprising anorganoaluminum compound with the following formula:Al(X⁵)_(n)(X⁶)_(3-n); wherein (X⁵) is a hydrocarbyl having from 1 toabout 20 carbon atoms; (X⁶) is an alkoxide or aryloxide, any one ofwhich having from 1 to about 20 carbon atoms, halide, or hydride; and nis a number from 1 to 3, inclusive.
 11. A catalyst compositioncomprising: a) a transition metal compound with the following formula:

wherein: M is titanium, zirconium, or hafnium; the group

is an anionic group selected from cyclodiphosphazanes, bis-phenoxides,N-alkoxy-β-ketoiminates, bis(phenoxy)diamides, diamidoamines,β-Diketonates, cyclodisilazanes, anilidoboranes, diamides, tridentatediamides, pyridine diamides, β-diketiminates, β-ketoiminates,amidinates, salicylaldiminates, substituted cyclodiphosphazanes,substituted bis-phenoxides, substituted N-alkoxy-β-ketoiminates,substituted bis(phenoxy)diamides, substituted diamidoamines, substitutedβ-Diketonates, substituted cyclodisilazanes, substituted anilidoboranes,substituted diamides, substituted tridentate diamides, substitutedpyridine diamides, substituted β-diketiminates, substitutedβ-ketoiminates, substituted amidinates, substituted salicylaldiminates,and mixtures thereof; a is 1, 2, 3, or 4; (Z) and (Z′) are independentlyan aliphatic group, an aromatic group, a cyclic group, a combination ofaliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogengroup, a phosphorus group, an arsenic group, a carbon group, a silicongroup, a germanium group, a tin group, a lead group, a boron group, analuminum group, an inorganic group, an organometallic group, or asubstituted derivative thereof, any one of which having from 1 to about20 carbon atoms, or a halide; b is 0, 1 or 2, and c is 0, 1 or 2; L isselected from ethers, furans and nitrites; d is 0, 1, or 2; b) achemically-treated solid oxide comprising a solid oxide treated with anelectron-withdrawing anion; wherein the solid oxide is silica, alumina,silica-alumina, aluminum phosphate, heteropolytungstates, titania,zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or mixturesthereof, and the electron-withdrawing anion is fluoride, chloride,bromide, phosphate, triflate, bisulfate, sulfate, or any combinationthereof; and optionally c) an organoaluminum compound with the followingformula:Al(X⁵)_(n)(X⁶)_(3-n); wherein (X⁵) is a hydrocarbyl having from 1 toabout 20 carbon atoms; (X⁶) is an alkoxide or aryloxide, any one ofwhich having from 1 to about 20 carbon atoms, halide, or hydride; and nis a number from 1 to 3, inclusive.
 12. The catalyst composition ofclaim 11, wherein the chemically-treated solid oxide further comprises ametal or metal ion.
 13. The catalyst composition of claim 11, whereinthe chemically-treated solid oxide further comprises zinc, nickel,vanadium, silver, copper, gallium, tin, tungsten, molybdenum, or anycombination thereof.
 14. The catalyst composition of claim 12, whereinthe chemically-treated solid oxide comprises a zinc-impregnatedchlorided alumina, zinc-impregnated fluorided alumina, zinc-impregnatedchlorided silica-alumina, zinc-impregnated fluorided silica-alumina,zinc-impregnated sulfated alumina, or any combination thereof.
 15. Acatalyst composition comprising: a) a transition metal compound with thefollowing formula:

wherein; M is titanium, zirconium, or hafnium; X is independentlynitrogen, oxygen, phosphorus or sulfur; Y is independently nitrogen,oxygen, phosphorus or sulfur; each substituent R_(n) on X or Y, isindependently an aliphatic group, an aromatic group, a cyclic group, acombination of aliphatic and cyclic groups, or a substituted derivativethereof, any one of which having from 1 to about 20 carbon atoms; adivalent bridging group, E, connecting X and Y, comprising P(NR)₂P,Ar(R)_(w)CH₂(R)_(w)Ar, Ar(R)_(w)S(R)_(w)Ar, C₂H₄NC(R)CH(R)C,Ar(R)_(w)CH₂N(R)C₂H₄N(R)CH₂Ar(R)_(w), C₂H₄NHC₂H₄, C₂H₄N(R)C₂H₄,Si(R)(NR)₂(R)Si, C(R¹)C(R²)C(R¹), B(NR₂)(NR₂)B, C₃H₆, C₂H₄OC₂H₄,CH₂(C₅H₃N)CH₂, C(R²)C(R³)C(R²), C(R), or CHAr(R)_(w), wherein R, R¹, R²,R³, or R′, is independently an alkyl, cycloalkyl, aryl, aralkyl,substituted alkyl, substituted aryl, or substituted aralkyl, any one ofwhich having from 1 to about 20 carbon atoms, wherein Ar is an aromaticgroup and (R)_(w) is independently an aliphatic group, an aromaticgroup, a cyclic group, a combination of aliphatic and cyclic groups, ora substituted derivative thereof, any one of which having from 1 toabout 20 carbon atoms, and where w is from 0-5; a is 1, 2, 3, or“Industrial Property Law 19039”4; (Z) and (Z′) are independently analiphatic group, an aromatic group, a cyclic group, a combination ofaliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogengroup, a phosphorus group, an arsenic group, a carbon group, a silicongroup, a germanium group, a tin group, a lead group, a boron group, analuminum group, an inorganic group, an organometallic group, or asubstituted derivative thereof, any one of which having from 1 to about20 carbon atoms; or a halide; b is 0, 1 or 2, and c is 0, 1 or 2; L isselected from ethers, furans and nitriles; d is 0, 1, or 2; b) achemically-treated solid oxide comprising a solid oxide treated with anelectron-withdrawing anion, wherein the solid oxide is silica, alumina,silica-alumina, aluminum phosphate, heteropolytungstates, titania,zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or mixturesthereof; and the electron-withdrawing anion is fluoride, chloride,bromide, phosphate, triflate, bisulfate, sulfate, or combinationsthereof; and c) an organoaluminum compound with the following formula:Al(X⁵)_(n)(X⁶)_(3-n); wherein (X⁵) is a hydrocarbyl having from 1 toabout 20 carbon atoms; (X⁶) is an alkoxide or aryloxide, any one ofwhich having from 1 to about 20 carbon atoms, halide, or hydride; and nis a number from 1 to 3, inclusive.
 16. The catalyst composition ofclaim 15, wherein the organoalumium compound is trimethylaluminum (TMA)triethylaluminum (TEA), tripropylaluminum, diethylaluminum ethoxide,tributylaluminum, disobutylaluminum hydride, triisobutylaluminum(TIBAL), diethylaluminum chloride, or any combination thereof.
 17. Thecatalyst composition of claim 15, wherein the weight ratio of theorganoalumium compound to chemically-treated solid oxide is from about5:1 to about 1:1000.
 18. The catalyst composition of claim 15, whereinthe weight ratio of the chemically-treated solid oxide to the transitionmetal compound is from about 10,000:1 to about 1:1.
 19. The catalystcomposition of claim 15, wherein the chemically-treated solid oxide isfluorided alumina, chlorided alumina, bromided alumina, fluoridedsilica-alumina, chlorided silica-alumina, sulfated alumina, sulfatedsilica-alumina, or a combination thereof.
 20. A process to produce thecatalyst composition of claim 1 comprising contacting the transitionmetal compound and the chemically-treated solid oxide.
 21. A process forpolymerizing olefins comprising contacting the catalyst composition ofclaim 1 with at least one type of olefin monomer in a polymerizationreactor under suitable conditions to produce a polymer.
 22. The processof claim 21 wherein the olefin monomer is ethylene.